Novel Insecticides

ABSTRACT

Compounds of the formula  
                 
in which 
         Z 1  is an oxygen atom; or a sulfur atom;    Z 2  is an oxygen atom; or a sulfur atom;    R 1  is an aryl or heteroaryl group, which is unsubstituted or substituted;    R 2  is hydrogen; or an organic substituent;    R 3  is hydrogen; or an organic substituent;    R 4  is hydrogen; or an organic substituent;    or R 3  and R 4 , taken together, form, together with the nitrogen atom, to which they are attached, a ring, which is unsubstituted or substituted;    R 5  is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R 8  or with a monovalent substituent attached to that atom of R 6 , via which atom R 6  is directly connected with the carbon atom, shown in the formula I, which carries R 5 , one additional bond;    R 6  and R 7 , taken together, form, together with the two carbon atoms, shown in the formula I, to which atoms they are attached, a bicyclic ring system, which ring system is carbocyclic or heterocyclic, which ring system is substituted, in the manner shown in the formula I, by the four substituents —N(R 2 )—C(=Z 1 )—R 1 , —C(=Z 2 )-N(R 3 )—R 4 , R 5  and R 8 , and which ring system is optionally further substituted;    and R 8  is hydrogen; or an unsubstituted or substituted alkyl group; or forms, taken together with R 5  or with a monovalent substituent attached to that atom of R 7 , via which atom R 7  is directly connected with the carbon atom, shown in the formula I, which carries R 8 , one additional bond, and, where appropriate, tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and can be prepared in a manner known per se.

The present invention relates to bicyclic bisamide derivatives, toprocesses for their preparation, to compositions comprising thosecompounds, and to their use for controlling insects or representativesof the order Acarina.

Bisamide derivatives with insecticidal action are known and described,for example, in US 2003/0229050.

There have now been found novel bicyclic bisamide derivatives withpesticidal properties. The present invention accordingly relates tocompounds of formula I

in which

Z₁ is an oxygen atom; or a sulfur atom;

Z₂ is an oxygen atom; or a sulfur atom;

R₁ is an aryl or heteroaryl group, which is unsubstituted orsubstituted;

R₂ is hydrogen; or an organic substituent;

R₃ is hydrogen; or an organic substituent;

R₄ is hydrogen; or an organic substituent;

or R₃ and R₄, taken together, form, together with the nitrogen atom, towhich they are attached, a ring, which is unsubstituted or substituted;

R₅ is hydrogen; or an unsubstituted or substituted alkyl group; orforms, taken together with R₈ or with a monovalent substituent attachedto that atom of R₆, via which atom R₆ is directly connected with thecarbon atom, shown in the formula I, which carries R₅, one additionalbond;

R₆ and R₇, taken together, form, together with the two carbon atoms,shown in the formula I, to which atoms they are attached, a bicyclicring system, which ring system is carbocyclic or heterocyclic, whichring system is substituted, in the manner shown in the formula I, by thefour substituents —N(R₂)—C(=Z₁)-R₁, —C(=Z₂)-N(R₃)—R₄, R₅ and R₈, andwhich ring system is optionally further substituted;

and R₈ is hydrogen; or an unsubstituted or substituted alkyl group; orforms, taken together with R₅ or with a monovalent substituent attachedto that atom of R₇, via which atom R₇ is directly connected with thecarbon atom, shown in the formula I, which carries R₈, one additionalbond,

in free form or in salt form, where appropriate to tautomers, in freeform or in salt form, of these compounds, to a process for thepreparation and to the use of these compounds and tautomers, topesticidal compositions whose active ingredient is selected from amongstthese compounds and tautomers, in each case in free form or inagrochemically utilizable salt form, to a process for the preparationand to the use of these compositions, to plant propagation materialtreated with these compositions, to a method of controlling pests withthese active ingredients and compositions, to intermediates, in freeform or in salt form, for the preparation of these compounds, whereappropriate to tautomers, in free form or in salt form, of theseintermediates, and to a process for the preparation and to the use ofthese intermediates.

In some cases, the compounds of formula I can exist as tautomers. Forexample, if in the compounds of formula I the substituent—N(R₂)—C(=Z₁)-R₁ is —N(R₂)—C(═O)—R₁ and R₂ is hydrogen, correspondingcompounds of formula I, i.e. those in which —N(R₂)—C(=Z₁)—R₁ is—N(H)—C(═O)—R₁, can be in equilibrium with the respective tautomers, inwhich the respective substituent has the tautomeric structure—N═C(OH)—R₁. Accordingly, the compounds of formula I hereinabove andhereinbelow are to be understood as including such tautomers, whereappropriate, even though the latter are not mentioned specifically ineach individual case.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine. Where appropriate, thecorresponding internal salts can furthermore be formed. Preferred withinthe scope of the invention are agrochemically advantageous salts;however, the invention also encompasses salts which have disadvantagefor agrochemical use, for example salts which are toxic to bees or fish,and which are employed, for example, for the isolation or purificationof free compounds of formula I or agrochemically utilizable saltsthereof. Owing to the close relationship between the compounds offormula I in free form and in the form of their salts, for the purposesof the invention the free compounds of formula I or their saltshereinabove and hereinbelow are respectively to be understood asincluding, where appropriate, the corresponding salts or the freecompounds of formula I. The same applies analogously to tautomers ofcompounds of formula I and salts thereof. In general, the free form ispreferred in each case.

Preferably the invention relates (2) to a compound according to (1) offormula I, in which

Z₁ is an oxygen atom; or a sulfur atom;

Z₂ is an oxygen atom; or a sulfur atom;

R₁ is a phenyl or naphthyl group, which is substituted independently by1 or 2 substituents R_(a) and optionally further substitutedindependently by 1 to 3 substituents R_(b);

R_(a) is cyano; nitro; halogen; C₁-C₆alkyl; halo-C₁-C₆alkyl;C₁-C₆alkoxy-C₁-C₆alkyl; C₂-C₆alkenyl; halo-C₂-C₆alkenyl; C₂-C₆alkynyl;halo-C₂-C₆alkynyl; C₃-C₆cycloalkyl; C₆cycloalkyl; hydroxy; C₁-C₆alkoxy;halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; mercapto; C₁-C₆alkylthio;halo-C₁-C₆alkylthio; C₁-C₆alkylsulfinyl; halo-C₁-C₆alkylsulfinyl;C₁-C₆alkylsulfonyl; halo-C₁-C₆alkylsulfonyl; amino; C₁-C₆alkylamino;halo-C₁-C₆alkylamino; di-C₁-C₆alkylamino, in which the two alkyl groupsare the same or different or, taken together, form, together with thenitrogen atom, to which they are attached, a ring containing 1 ringnitrogen atom and 2 to 12 ring carbon atoms and optionally 1 furtherring hetero atom, which then replaces 1 ring carbon atom and is selectedfrom the group, consisting of an oxygen, a sulfur and a nitrogen atom,which ring is unsubstituted or substituted independently by 1 to 4substituents, selected from the group, consisting of cyano, nitro,halogen, C₁-C₄alkyl and C₁-C₄alkoxy; di-(halo-C₁-C₆alkyl)-amino, inwhich the two haloalkyl groups are the same or different;C₃-C₆cycloalkylamino; N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino; carboxy;C₁-C₆alkoxycarbonyl; halo-C₁-C₆alkoxycarbonyl; aminocarbonyl;C₁-C₆alkylaminocarbonyl; halo-C₁-C₆alkylaminocarbonyl;di-C₁-C₆alkylaminocarbonyl, in which the two alkyl groups are the sameor different or, taken together, form, together with the nitrogen atom,to which they are attached, a ring containing 1 ring nitrogen atom and 2to 12 ring carbon atoms and optionally 1 further ring hetero atom, whichthen replaces 1 ring carbon atom and is selected from the group,consisting of an oxygen, a sulfur and a nitrogen atom, which ring isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of cyano, nitro, halogen, C₁-C₄alkyland C₁-C₄alkoxy; di-(halo-C₁-C₆alkyl)-aminocarbonyl, in which the twohaloalkyl groups are the same or different; C₁-C₆alkylcarbonyl;halo-C₁-C₆alkylcarbonyl; or tri-C₁-C₆alkylsilyl, in which the threealkyl groups are the same or different;

or 2 substituents R_(a), which are attached to adjacent carbon atoms,taken together, are —(CH₂—)₃; —(CH₂—)₄; —(CH₂—)₅; —(CH═CH—)₂; —OCH₂O—;—O—(CH₂—)₂O—; —O—(CF₂—)₂; or —O—(CF₂—)₂O—;

R_(b) is halogen; C₁-C₆alkyl; C₂-C₆alkenyl; C₂-C₆alkynyl;C₃-C₆cycloalkyl; C₁-C₆alkoxy; C₁-C₆alkoxycarbonyl; or a phenyl, benzyl,phenoxy or monocyclic or bicyclic heteroaryl group, which group isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of the substituents R_(a);

or R₁ is a monocyclic or bicyclic heteroaryl group, which isunsubstituted or substituted independently by 1 to 4 substituents R_(c);

R_(c) is a substituent R_(a); or a phenyl, benzyl, benzoyl, phenoxy ormonocyclic or bicyclic heteroaryl group, which group is unsubstituted orsubstituted independently by 1 to 4 substituents, selected from thegroup, consisting of the substituents R_(a);

R₂ is hydrogen; a C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl orC₃-C₆cycloalkyl group, which group is unsubstituted or substitutedindependently by one or more substituents, selected from the group,consisting of the substituents R_(a); a group C(═O)R_(d); or a groupC(═S)R_(d);

R_(d) is a substituent R₁; C₁-C₆alkyl; halo-C₁-C₆alkyl;C₁-C₆alkoxy-C₁-C₆alkyl; a group CH₂R₁; a group CH₂OR₁; a group CH₂SR₁; agroup CH₂NHR₁, which group is optionally further substituted at thenitrogen atom by C₁-C₆alkyl or halo-C₁-C₆alkyl; C₂-C₆alkenyl;halo-C₂-C₆alkenyl; C₂-C₆alkynyl; halo-C₂-C₆alkynyl; C₃-C₆cycloalkyl;halo-C₃-C₆cycloalkyl; C₁-C₆alkoxy; halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; agroup OR₁; C₁-C₆alkylthio; halo-C₁-C₆alkylthio; a group SR₁;C₁-C₆alkylamino; halo-C₁-C6alkylamino; di-C₁-C₆alkylamino, in which thetwo alkyl groups are the same or different or, taken together, form,together with the nitrogen atom, to which they are attached, a ringcontaining 1 ring nitrogen atom and 2 to 12 ring carbon atoms andoptionally 1 further ring hetero atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;di-(halo-C₁-C₆alkyl)-amino, in which the two haloalkyl groups are thesame or different; C₃-C₆cycloalkylamino;N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino; or a group NHR₁, which groupis optionally further substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁-C₆alkyl;

R₃ is hydrogen; a C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl orC₃-C₆cycloalkyl group, which group is unsubstituted or substitutedindependently by one or more substituents, selected from the group,consisting of the substituents R_(a); C₁-C₆alkoxy; halo-C₁-C₆alkoxy;C₃-C₆cycloalkoxy; C₁-C₆alkylthio; halo-C₁-C₆alkylthio; C₁-C₆alkylamino;halo-C₁-C₆alkoxy; di-C₁-C₆alkylamino, in which the two alkyl groups arethe same or different or, taken together, form, together with thenitrogen atom, to which they are attached, a ring containing 1 ringnitrogen atom and 2 to 12 ring carbon atoms and optionally 1 furtherring hetero atom, which then replaces 1 ring carbon atom and is selectedfrom the group, consisting of an oxygen, a sulfur and a nitrogen atom,which ring is unsubstituted or substituted independently by 1 to 4substituents, selected from the group, consisting of cyano, nitro,halogen, C₁-C₄alkyl and C₁-C₄alkoxy; di-(halo-C₁-C₆alkyl)-amino, inwhich the two haloalkyl groups are the same or different;C₃-C₆cycloalkylamino; N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino;C₁-C₆alkoxycarbonyl; halo-C₁-C₆alkoxycarbonyl; C₁-C₆alkylcarbonyl orhalo-C₁-C₆alkylcarbonyl;

R₄ is hydrogen; a substituent R₁; a substituent R_(e); a C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group, which group isunsubstituted or substituted independently by one or more substituents,selected from the group, consisting of the substituents R_(a), thesubstituents R_(e) and a phenyl, benzoyl, phenoxy or monocyclic orbicyclic heteroaryl group, which group is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of the substituents R_(c); a group CH₂OR₁; a group CH₂SR₁; agroup CH₂NHR₁, which group is optionally further substituted at thenitrogen atom by C₁-C₆alkyl or halo-C₁-C₆alkyl; C₁-C₆alkoxy;halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; a group OR₁; C₁-C₆alkylthio;halo-C₁-C₆alkylthio; a group SR₁; C₁-C₆alkylsulfinyl;halo-C₁-C₆alkylsulfinyl; C₁-C₆alkylsulfonyl; halo-C₁-C₆alkylsulfonyl;C₁-C₆alkylamino; halo-C₁-C₆alkylamino; di-C₁-C₆alkylamino, in which thetwo alkyl groups are the same or different or, taken together, form,together with the nitrogen atom, to which they are attached, a ringcontaining 1 ring nitrogen atom and 2 to 12 ring carbon atoms andoptionally 1 further ring hetero atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;di-(halo-C₁-C₆alkyl)-amino, in which the two haloalkyl groups are thesame or different; C₃-C₆cycloalkylamino;N—(C₁-C₆alkyl)-N-(C₃-C₆cycloalkyl)-amino; a group NHR₁, which group isoptionally further substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁-C₆alkyl; a group C(═O)R_(d); a group C(═O)R_(e); a groupC(═S)R_(d); or a group C(═S)R_(e);

R_(e) is a carbocyclyl or heterocyclyl group, which group is monocyclicor bicyclic and is non-aromatic, in which group 1 or 2 of the ringmembers are optionally selected from the group, consisting of the groupsC(═O), S(═O) and S(═O)₂, and which group is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;

or R₃ and R₄, taken together, form, together with the nitrogen atom, towhich they are attached, a ring containing 1 ring nitrogen atom and 2 to6 ring carbon atoms and optionally 1 further ring hetero atom, whichthen replaces 1 ring carbon atom and is selected from the group,consisting of an oxygen, a sulfur and a nitrogen atom, which ring isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of cyano, nitro, halogen, C₁-C₄alkyland C₁-C₄alkoxy;

R₅ is hydrogen; C₁-C₆alkyl; or halo-C₁-C₆alkyl; or has one of themeanings defined hereinafter;

R₆ and R₇, taken together, are either a group of the formula

in which G₁ is attached to the carbon atom, shown in the formula I, thatcarries R₅; and in which G₅ is attached to the carbon atom, shown in theformula I, that carries R₈; or are a group of the formula

in which G₁ is attached to the carbon atom, shown in the formula I, thatcarries R₅; and in which G₄ is attached to the carbon atom, shown in theformula I, that carries R₈; or are a group of the formula

in which G₁ is attached to the carbon atom, shown in the formula I, thatcarries R₅; and in which G₃ is attached to the carbon atom, shown in theformula I, that carries R₈;

in which formulae Ia, Ib and Ic either a is 0; f is 0; and G₁ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or a is 0; f is 1; and G₁ is a nitrogen atom; or a is 1; fis 1; and G₁ is a carbon atom; either b is 0; g is 0; and G₂ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or b is 0; g is 1; and G₂ is a nitrogen atom; or b is 1; gis 1; and G₂is a carbon atom; and either c is 0; h is 0; and G₃ is agroup C(═O); a group C(═S); an oxygen atom; a sulfur atom; a groupS(═O); or a group S(═O)₂; or c is 0; h is 1; and G₃ is a nitrogen atom;or c is 1; h is 1; and G₃ is a carbon atom;

in which formulae Ia and Ib either d is 0; i is 0; and G₄ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or d is 0; i is 1; and G₄ is a nitrogen atom; or d is 1; iis 1; and G₄ is a carbon atom;

in which formula Ia either e is 0; j is 0; and G₅ is a group C(═O); agroup C(═S); an oxygen atom; a sulfur atom; a group S(═O); or a groupS(═O)₂; or e is 0; j is 1; and G₅ is a nitrogen atom; or e is 1; j is 1;and G₅ is a carbon atom;

in which formula la either f is 1; g is 1; and R₁₂ and R₂₂, takentogether, are either a group of the formula

in which G₆ is attached to G₁; and in which G₁₀ is attached to G₂; orare a group of the formula

in which G₆ is attached to G₁; and in which G₉ is attached to G₂; or area group of the formula

in which G₆ is attached to G₁; and in which G₈ is attached to G₂;

or g is 1; h is 1; and R₂₂ and R₃₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₂; and in which G₁₀ isattached to G₃; or a a group of the formula Ie, in which G₆ is attachedto G₂; and in which G₉ is attached to G₃; or are a group of the formulaIf, in which G₆ is attached to G₂; and in which G₈ is attached to G₃;

or h is 1; i is 1; and R₃₂ and R₄₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₃; and in which G₁₀ isattached to G₄; or are a group of the formula Ie, in which G₆ isattached to G₃; and in which G₉ is attached to G₄; or are a group of theformula If, in which G₆ is attached to G₃; and in which G₈ is attachedto G₄;

or i is 1; j is 1; and R₄₂ and R₅₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₄; and in which G₁₀ isattached to G₅; or are a group of the formula Ie, in which G₆ isattached to G₄; and in which G₉ is attached to G₅; or are a group of theformula If, in which G₆ is attached to G₄; and in which G₈ is attachedto G₅;

in which formula Ib either f is 1; g is 1; and R₁₂ and R₂₂, takentogether, are either a group of the formula Id, in which G₆ is attachedto G₁; and in which G₁₀ is attached to G₂; or are a group of the formulaIe, in which G₆ is attached to G₁; and in which G₉ is attached to G₂; orare a group of the formula If, in which G₆ is attached to G₁; and inwhich G₈ is attached to G₂;

or g is 1; h is 1; and R₂₂ and R₃₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₂; and in which G₁₀ isattached to G₃; or are a group of the formula Ie, in which G₆ isattached to G₂; and in which G₉ is attached to G₃; or are a group of theformula If, in which G₆ is attached to G₂; and in which G₈ is attachedto G₃;

or h is 1; i is 1; and R₃₂ and R₄₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₃; and in which G₁₀ isattached to G₄; or are a group of the formula Ie, in which G₆ isattached to G₃; and in which G₉ is attached to G₄; or are a group of theformula If, in which G₆ is attached to G₃; and in which G₈ is attachedto G₄;

in which formula Ic either f is 1; g is 1; and R₁₂ and R₂₂, takentogether, are either a group of the formula Id, in which G₆ is attachedto G₁; and in which G₁₀ is attached to G₂; or are a group of the formulaIe, in which G₆ is attached to G₁; and in which G₉ is attached to G₂; orare a group of the formula If, in which G₆ is attached to G₁; and inwhich G₈ is attached to G₂;

or g is 1; h is 1; and R₂₂ and R₃₂, taken together, are either a groupof the formula Id, in which G₆ is attached to G₂; and in which G₁₀ isattached to G₃; or are a group of the formula Ie, in which G₆ isattached to G₂; and in which G₉ is attached to G₃; or are a group of theformula If, in which G₆ is attached to G₂; and in which G₈ is attachedto G₃;

in which formulae Ia, Ib and Ic the atoms G₁ and G₂ can be connected byone additional bond, which bond, if present, is represented by a firstsubstituent, which is R₁₂, if G₁ is a nitrogen atom, and which is R₁₁ orR₁₂, if G₁ is a carbon atom, and a second substituent, which is R₂₂, ifG₂ is a nitrogen atom, and which is R₂₁ or R₂₂, if G₂ is a carbon atom,taken together;

in which formulae Ia, Ib and Ic the atoms G₂ and G₃ can be connected byone additional bond, which bond, if present, is represented by a firstsubstituent, which is R₂₂, if G₂ is a nitrogen atom, and which is R₂₁ orR₂₂, if G₂ is a carbon atom, and a second substituent, which is R₃₂, ifG₃ is a nitrogen atom, and which is R₃₁ or R₃₂, if G₃ is a carbon atom,taken together;

in which formulae Ia and Ib the atoms G₃ and G₄ can be connected by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₃₂, if G₃ is a nitrogen atom, and which is R₃₁ orR₃₂, if G₃ is a carbon atom, and a second substituent, which is R₄₂, ifG₄ is a nitrogen atom, and which is R₄₁ or R₄₂, if G₄ is a carbon atom,taken together;

in which formula la the atoms G₄ and G₅ can be connected by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₄₂, if G₄ is a nitrogen atom, and which is R₄₁ orR₄₂, if G₄ is a carbon atom, and a second substituent, which is R₅₂, ifG₅ is a nitrogen atom, and which is R₅₁ or R₅₂, if G₅ is a carbon atom,taken together;

in which formulae Ia, Ib and Ic the atom G₁ can be connected with thecarbon atom, shown in the formula I, that carries R₅, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₁₂, if G₁ is a nitrogen atom, and which is R₁₁ or R₁₂, if G₁is a carbon atom, and a second substituent, which is R₅, taken together;

in which formula la the atom G₅ can be connected with the carbon atom,shown in the formula I, that carries R₈, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₅₂,if G₅ is a nitrogen atom, and which is R₅₁ or R₅₂, if G₅ is a carbonatom, and a second substituent, which is R₈, taken together;

in which formula Ib the atom G₄ can be connected with the carbon atom,shown in the formula I, that carries R₈, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₄₂,if G₄ is a nitrogen atom, and which is R₄₁ or R₄₂, if G₄ is a carbonatom, and a second substituent, which is R₈, taken together;

in which formula Ic the atom G₃ can be connected with the carbon atom,shown in the formula I, that carries R₈, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₃₂,if G₃ is a nitrogen atom, and which is R₃₁ or R₃₂, if G₃ is a carbonatom, and a second substituent, which is R₈, taken together;

in which formula la each of those substituents, selected from the group,consisting of the substituents R₁₁, R₁₂, R₂₁, R₂₂, R₃₁, R₃₂, R₄₁, R₄₂,R₅₁ and R₅₂, which are different from the two substituents, which, takentogether, form the group of the formula Id, Ie or If, and different fromany first substituent, if present, as defined hereinbefore for theformula Ia, and from any second substituent, if present, as definedhereinbefore for the formula Ia, is independently selected from thegroup, consisting of the substituents R₁;

in which formula Ib each of those substituents, selected from the group,consisting of the substituents R₁₁, R₁₂, R₂₁, R₂₂, R₃₁, R₃₂, R₄₁ andR₄₂, which are different from the two substituents, which, takentogether, form the group of the formula Id, Ie or If, and different fromany first substituent, if present, as defined hereinbefore for theformula Ib, and from any second substituent, if present, as definedhereinbefore for the formula Ib, is independently selected from thegroup, consisting of the substituents R_(f);

in which formula Ic each of those substituents, selected from the group,consisting of the substituents R₁₁, R₁₂, R₂₁, R₂₂, R₃₁ and R₃₂, whichare different from the two substituents, which, taken together, form thegroup of the formula Id, Ie or If, and different from any firstsubstituent, if present, as defined hereinbefore for the formula Ic, andfrom any second substituent, if present, as defined hereinbefore for theformula Ic, is independently selected from the group, consisting of thesubstituents R_(f);

R_(f) is hydrogen; or a substituent R_(g); the total number of thesubstituents R_(g), if present, having an upper limit of 5 for a groupof the formula Ia; of 4 for a group of the formula Ib; and of 3 for agroup of the formula Ic; which total number can, however, be limited fora specific group of the formula Ia, Ib or Ic to a value lower than theupper limit mentioned hereinbefore, which value is then equal to thenumber of the positions available for the substitution by a substituentR_(g) in this specific group;

R_(g) is either attached to a carbon atom and then selected from thegroup, consisting of the substituents R_(g-c); or attached to a nitrogenatom and then selected from the group, consisting of the substituentsR_(g-n);

R_(g-c) is a substituent R_(c);

R_(g-n) is cyano; nitro; C₁-C₆alkyl; halo-C₁-C₆alkyl;C₁-C₆alkoxy-C₁-C₆alkyl; C₂-C₆alkenyl; halo-C₂-C₆alkenyl; C₂-C₆alkynyl;halo-C₂-C₆alkynyl; C₃-C₆cycloalkyl; halo-C₃-C₆cycloalkyl; C₁-C₆alkoxy;halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; C₁-C₆alkylthio, halo-C₁-C₆alkylthio;C₁-C₆alkylsulfinyl; halo-C₁-C₆alkylsulfinyl; C₁-C₆alkylsulfonyl;halo-C₁-C₆alkylsulfonyl; amino; C₁-C₆alkylamino; halo-C₁-C₆alkylamino;di-C₁-C₆alkylamino, in which the two alkyl groups are the same ordifferent or, taken together, form, together with the nitrogen atom, towhich they are attached, a ring containing 1 ring nitrogen atom and 2 to12 ring carbon atoms and optionally 1 further ring hetero atom, whichthen replaces 1 ring carbon atom and is selected from the group,consisting of an oxygen, a sulfur and a nitrogen atom, which ring isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of cyano, nitro, halogen, C₁-C₄alkyland C₁-C₄alkoxy; di-(halo-C₁-C₆alkyl)-amino, in which the two haloalkylgroups are the same or different; C₃-C₆cycloalkylamino;N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino; C₁-C₆alkoxycarbonyl;halo-C₁-C₆alkoxycarbonyl; aminocarbonyl; C₁-C₆alkylaminocarbonyl;halo-C₁-C₆alkylaminocarbonyl; di-C₁-C₆alkylaminocarbonyl, in which thetwo alkyl groups are the same or different or, taken together, form,together with the nitrogen atom, to which they are attached, a ringcontaining 1 ring nitrogen atom and 2 to 12 ring carbon atoms andoptionally 1 further ring hetero atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;di-(halo-C₁-C₆alkyl)-aminocarbonyl, in which the two haloalkyl groupsare the same or different; C₁-C₆alkylcarbonyl; halo-C₁-C₆alkylcarbonyl;tri-C₁-C₆alkylsilyl, in which the three alkyl groups are the same ordifferent; or a phenyl, benzyl, benzoyl, phenoxy or monocyclic orbicyclic heteroaryl group, which group is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of the substituents R_(a);

in which formulae Id, Ie and If either k is 0; p is 0; and G₆ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or k is 0; p is 1; and G₆ is a nitrogen atom; or k is 1; pis 1; and G₆ is a carbon atom; either I is 0; q is 0; and G₇ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or 1 is 0; q is 1; and G₇ is a nitrogen atom; or I is 1; qis 1; and G₇ is a carbon atom; and either m is 0; r is 0; and G₈ is agroup C(═O); a group C(═S); an oxygen atom; a sulfur atom; a groupS(═O); or a group S(═O)₂; or m is 0; r is 1; and G₈ is a nitrogen atom;or m is 1; r is 1; and G₈ is a carbon atom;

in which formulae Id and Ie either n is 0; s is 0; and G₉ is a groupC(═O); a group C(═S); an oxygen atom; a sulfur atom; a group S(═O); or agroup S(═O)₂; or n is 0; s is 1; and G₉ is a nitrogen atom; or n is 1; sis 1; and G₉ is a carbon atom;

in which formula Id either o is 0; t is 0; and G₁₀ is a group C(═O); agroup C(═S); an oxygen atom; a sulfur atom; a group S(═O); or a groupS(═O)₂; or o is 0; t is 1; and G₁₀ is a nitrogen atom; or o is 1; t is1; and G₁₀ is a carbon atom;

in which formulae Id, Ie and If the atoms G₆ and G₇ can be connected byone additional bond, which bond, if present, is represented by a firstsubstituent, which is R₆₂, if G₆ is a nitrogen atom, and which is R₆₁ orR₆₂, if G₆ is a carbon atom, and a second substituent, which is R₇₂, ifG₇ is a nitrogen atom, and which is R₇₁ or R₇₂, if G₇ is a carbon atom,taken together;

in which formulae Id, Ie and If the atoms G₇ and G₈ can be connected byone additional bond, which bond, if present, is represented by a firstsubstituent, which is R₇₂, if G₇ is a nitrogen atom, and which is R₇₁ orR₇₂, if G₇ is a carbon atom, and a second substituent, which is R₈₂, ifG₈ is a nitrogen atom, and which is R₈₁ or R₈₂, if G₈ is a carbon atom,taken together;

in which formulae Id and Ie the atoms G₈ and G₉ can be connected by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₈₂, if G₈ is a nitrogen atom, and which is R₈₁ orR₈₂, if G₈ is a carbon atom, and a second substituent, which is R₉₂, ifG₉ is a nitrogen atom, and which is R₉₁ or R₉₂, if G₉ is a carbon atom,taken together;

in which formula Id the atoms G₉ and G₁₀ can be connected by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₉₂, if G₉ is a nitrogen atom, and which is R₉₁ orR₉₂, if G₉ is a carbon atom, and a second substituent, which is R₁₀₂, ifG₁₀ is a nitrogen atom, and which is R₁₀₁ or R₁₀₂, if G₁₀ is a carbonatom, taken together;

in which formulae Id, Ie and If the atom G₆ can be connected either withthe atom G₁, shown in the formulae Ia, Ib and Ic, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₆₂, if G₆ is a nitrogen atom, and which is R₆₁ or R₆₂, if G₆is a carbon atom, and a second substituent, which is R₁₂, if G₁ is anitrogen atom, and which is R₁₁ or R₁₂, if G₁ is a carbon atom, takentogether;

or with the atom G₂, shown in the formulae Ia, Ib and Ic, by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₆₂, if G₆ is a nitrogen atom, and which is R₆₁ orR₆₂, if G₆ is a carbon atom, and a second substituent, which is R₂₂, ifG₂ is a nitrogen atom, and which is R₂₁ or R₂₂, if G₂ is a carbon atom,taken together;

or with the atom G₃, shown in the formulae Ia and Ib, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₆₂, if G₆ is a nitrogen atom, and which is R₆₁ or R₆₂, if G₆is a carbon atom, and a second substituent, which is R₃₂, if G₃ is anitrogen atom, and which is R₃₁ or R₃₂, if G₃ is a carbon atom, takentogether;

or with the atom G₄, shown in the formula Ia, by one additional bond,which bond, if present, is represented by a first substituent, which isR₆₂, if G₆ is a nitrogen atom, and which is R₆₁ or R₆₂, if G₆ is acarbon atom, and a second substituent, which is R₄₂, if G₄ is a nitrogenatom, and which is R₄₁ or R₄₂, if G₄ is a carbon atom, taken together;

in which formula Id the atom G₁₀ can be connected either with the atomG₂, shown in the formulae Ia, Ib and Ic, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₁₀₂,if G₁₀ is a nitrogen atom, and which is R₁₀₁ or R₁₀₂, if G₁₀ is a carbonatom, and a second substituent, which is R₂₂, if G₂ is a nitrogen atom,and which is R₂₁ or R₂₂, if G₂ is a carbon atom, taken together;

or with the atom G₃, shown in the formulae Ia, Ib and Ic, by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₁₀₂, if G₁₀ is a nitrogen atom, and which is R₁₀₁or R₁₀₂, if G₁₀ is a carbon atom, and a second substituent, which isR₃₂, if G₃ is a nitrogen atom, and which is R₃₁ or R₃₂, if G₃ is acarbon atom, taken together;

or with the atom G₄, shown in the formulae Ia and Ib, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₁₀₂, if G₁₀ is a nitrogen atom, and which is R₁₀₁ or R₁₀₂, ifG₁₀ is a carbon atom, and a second substituent, which is R₄₂, if G₄ is anitrogen atom, and which is R₄₁ or R₄₂, if G₄ is a carbon atom, takentogether;

or with the atom G₅, shown in the formula Ia, by one additional bond,which bond, if present, is represented by a first substituent, which isR₁₀₂, if G₁₀ is a nitrogen atom, and which is R₁₀₁ or R₁₀₂, if G₁₀ is acarbon atom, and a second substituent, which is R₅₂, if G₅ is a nitrogenatom, and which is R₅₁ or R₅₂, if G₅ is a carbon atom, taken together;

in which formula Ie the atom G₉ can be connected either with the atomG₂, shown in the formulae Ia, Ib and Ic, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₉₂,if G₉ is a nitrogen atom, and which is R₉₁ or R₉₂, if G₉ is a carbonatom, and a second substituent, which is R₂₂, if G₂ is a nitrogen atom,and which is R₂₁ or R₂₂, if G₂ is a carbon atom, taken together;

or with the atom G₃, shown in the formulae Ia, Ib and Ic, by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₉₂, if G₉ is a nitrogen atom, and which is R₉₁ orR₉₂, if G₉ is a carbon atom, and a second substituent, which is R₃₂, ifG₃ is a nitrogen atom, and which is R₃₁ or R₃₂, if G₃ is a carbon atom,taken together;

or with the atom G₄, shown in the formulae Ia and Ib, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₉₂, if G₉ is a nitrogen atom, and which is R₉₁ or R₉₂, if G₉is a carbon atom, and a second substituent, which is R₄₂, if G₄ is anitrogen atom, and which is R₄₁ or R₄₂, if G₄ is a carbon atom, takentogether;

or with the atom G₅, shown in the formula Ia, by one additional bond,which bond, if present, is represented by a first substituent, which isR₉₂, if G₉ is a nitrogen atom, and which is R₉₁ or R₉₂, if G₉ is acarbon atom, and a second substituent, which is R₅₂, if G₅ is a nitrogenatom, and which is R₅₁ or R₅₂, if G₅ is a carbon atom, taken together;

in which formula If the atom G₈ can be connected either with the atomG₂, shown in the formulae Ia, Ib and Ic, by one additional bond, whichbond, if present, is represented by a first substituent, which is R₈₂,if G₈ is a nitrogen atom, and which is R₈₁ or R₈₂, if G₈ is a carbonatom, and a second substituent, which is R₂₂, if G₂ is a nitrogen atom,and which is R₂₁ or R₂₂, if G₂ is a carbon atom, taken together;

or with the atom G₃, shown in the formulae Ia, Ib and Ic, by oneadditional bond, which bond, if present, is represented by a firstsubstituent, which is R₈₂, if G₈ is a nitrogen atom, and which is R₈₁ orR₈₂, if G₈ is a carbon atom, and a second substituent, which is R₃₂, ifG₃ is a nitrogen atom, and which is R₃₁ or R₃₂, if G₃ is a carbon atom,taken together;

or with the atom G₄, shown in the formulae Ia and Ib, by one additionalbond, which bond, if present, is represented by a first substituent,which is R₈₂, if G₈ is a nitrogen atom, and which is R₈₁ or R₈₂, if G₈is a carbon atom, and a second substituent, which is R₄₂, if G₄ is anitrogen atom, and which is R₄₁ or R₄₂, if G₄ is a carbon atom, takentogether;

or with the atom G₅, shown in the formula Ia, by one additional bond,which bond, if present, is represented by a first substituent, which isR₈₂, if G₈ is a nitrogen atom, and which is R₈₁ or R₈₂, if G₈ is acarbon atom, and a second substituent, which is R₅₂, if G₅ is a nitrogenatom, and which is R₅₁ or R₅₂, if G₅ is a carbon atom, taken together;

in which formula Id each of those substituents, selected from the group,consisting of the substituents R₆₁, R₆₂, R₇₁, R₇₂, R₈₁, R₈₂, R₉₁, R₉₂,R₁₀₁, and R₁₀₂, which are different from any first substituent, ifpresent, as defined hereinbefore for the formula Id, and from any secondsubstituent, if present, as defined hereinbefore for the formula Id, isindependently selected from the group, consisting of the substituentsR_(h);

in which formula Ie each of those substituents, selected from the group,consisting of the substituents R₆₁, R₆₂, R₇₁, R₇₂, R₈₁, R₈₂, R₉₁ andR₉₂, which are different from any first substituent, if present, asdefined hereinbefore for the formula Ie, and from any secondsubstituent, if present, as defined hereinbefore for the formula Ie, isindependently selected from the group, consisting of the substituentsR_(i);

in which formula If each of those substituents, selected from the group,consisting of the substituents R₆₁, R₆₂, R₇₁, R₇₂, R₈₁ and R₈₂, whichare different from any first substituent, if present, as definedhereinbefore for the formula If, and from any second substituent, ifpresent, as defined hereinbefore for the formula If, is independentlyselected from the group, consisting of the substituents R_(h);

R_(h) is hydrogen; or a substituent R_(j); the total number of thesubstituents R_(j), if present, having an upper limit of 6 for a groupof the formula Id; and of 4 for a group of the formula If; which totalnumber can, however, be limited for a specific group of the formula Idor If to a value lower than the upper limit mentioned hereinbefore,which value is then equal to the number of the positions available forthe substitution by a substituent R_(j) in this specific group;

R_(i) is hydrogen; or a substituent R_(k); the total number of thesubstituents R_(k), if present, having an upper limit of 5; which totalnumber can, however, be limited for a specific group of the formula Ieto a value lower than the upper limit mentioned hereinbefore, whichvalue is then equal to the number of the positions available for thesubstitution by a substituent R_(k) in this specific group;

R_(j) is either attached to a carbon atom and then selected from thegroup, consisting of the substituents R_(j-c); or attached to a nitrogenatom and then selected from the group, consisting of the substituentsR_(j-n);

R_(j-c) is a substituent R_(c);

R_(j-n) is a substituent R_(g-n);

R_(k) is either attached to a carbon atom and then selected from thegroup, consisting of the substituents R_(k-c); or attached to a nitrogenatom and then selected from the group, consisting of the substituentsR_(k-n);

or 2 substituents R_(k), the first of which is attached to the atom G₆and is represented by R₆₂, if G₆ is a nitrogen atom, and by R₆₁ or R₆₂,if G₆ is a carbon atom, and the second of which is attached to the atomG₉ and is represented by R₉₂, if G₉ is a nitrogen atom, and by R₉₁ orR₉₂, if G₉ is a carbon atom, taken together, are —CH₂—; or —O—;

R_(k-c) is a substituent R_(c);

R_(k-n) is a substituent R_(g-n);

R₈ is hydrogen; C₁-C₆alkyl; or halo-C₁-C₆alkyl; or has one of themeanings defined hereinbefore or hereinafter;

or R₅ and R₈, taken together, are a bond;

with the proviso, that

(i) a ring oxygen atom, if present, is not directly connected with afurther ring oxygen atom, if any;

(ii) a ring carbon atom, selected from the group, consisting of G₁, G₂,G₃, G₄, G₅, G₆, G₇, G₈, G₉ and G₁₀, is, if present, not directlyconnected with any other atom by a triple bond or with any other 2different atoms by 2 double bonds;

(iii) not more than 6 of the variables G₁, G₂, G₃, G₄, G₅, G₆, G₇, G₈,G₉ and G₁₀ can, if present, be selected from the group, consisting of anoxygen atom, a sulfur atom, a group S(═O), a group S(═O)₂ and a nitrogenatom, each of the remaining of these variables, if any, being selectedfrom the group, consisting of a carbon atom, a group C(═O) and a groupC(═S), and not more than 3 of the said 6 variables can be selected fromthe group, consisting of an oxygen atom, a sulfur atom, a group S(═O)and a group S(═O)₂; and

(iv) unless otherwise defined hereinbefore, the meaning of a variable ata certain occurrence can be selected independently from the meaning ofthe same variable at any other occurrence, if any.

Unless otherwise defined, the general terms used hereinabove andhereinbelow have the meanings which follow.

Halogen—as a group per se and as a structural element of other groupsand compounds, such as haloalkyl—is, for example, fluorine, chlorine,bromine or iodine, in particular fluorine, chlorine or bromine, butespecially chlorine or bromine.

Unless otherwise defined, carbon-containing groups and compoundscomprise for example in each case 1 up to and including 15, preferably 1up to and including 10, especially 1 up to and including 8, inparticular 1 up to and including 5, especially 1 or 2, carbon atom(s).

Cycloalkyl—as a group per se and as a structural element of other groupsand compounds, such as halocycloalkyl—is, in each case with dueconsideration of the number of carbon atoms contained in each case inthe relevant group or compound, for example cyclopropyl, cyclobutyl,cyclopentyl or cyclohexyl.

Alkyl—as a group per se and as a structural element of other groups andcompounds, such as haloalkyl—is, in each case with due consideration ofthe number of carbon atoms contained in each case in the relevant groupor compound, either straight-chain, for example methyl, ethyl, propyl,butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl,sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl—as a group per se and as a structural element of other groupsand compounds, such as haloalkenyl—is, in each case with dueconsideration of the number of carbon atoms contained in each case inthe relevant group or compound, either straight-chain or branched andcomprises in each case 2 or more than 2 or preferably 1 carbon-carbondouble bond(s), the double bonds of these substituents being separatedfrom the remaining moiety of the compound I by preferably at least onesaturated carbon atom, and is, for example, allyl, propen-2-yl,methallyl, but-2-en-1-yl, but-3-en-1-yl or pent-4-en-1-yl.

Alkynyl—as a group per se and as a structural element of other groupsand compounds, such as haloalkynyl—is, in each case with dueconsideration of the number of carbon atoms contained in each case inthe relevant group or compound, either straight-chain or branched andcomprises in each case 2 or more than 2 or preferably 1 carbon-carbontriple bond(s), the triple bonds of these substituents being separatedfrom the remaining moiety of the compound I by preferably at least onesaturated carbon atom, and is, for example, propargyl, but-2-ynyl orbut-3-yn-2-yl.

Aryl is, for example, naphthyl or, preferably, phenyl.

Heteroaryl has, for example, an aromatic ring skeleton composed of aring having 5 or 6 ring members or of a combination of at least tworings having in each case independently of one another 5 or 6 ringmembers, where for example 1 up to and including 4 of the ring membersis (are) (a) heteroatom(s) selected from the group consisting ofnitrogen, oxygen and sulfur, and is, for example, pyridyl, thienyl,pyrazolyl, thiazolyl, thiadiazolyl, furyl, oxadiazolyl, indolizinyl,pyrimidyl, quinolyl or pteridinyl.

Non-aromatic heterocyclyl has, for example, a non-aromatic ring skeletoncomposed of a ring having 5 or 6 ring members or of a combination of atleast two rings having in each case independently of one another 5 or 6ring members, where for example 1 up to and including 4 of the ringmembers is (are) (a) heteroatom(s) selected from the group consisting ofnitrogen, oxygen and sulfur and is, for example, piperidyl, pyrrolinyl,tetrahydrofuryl or chromanyl.

Halogen-substituted carbon-containing groups and compounds, such ashaloalkyl, can be partially halogenated or perhalogenated, where, in thecase of polyhalogenation, the halogen substituents can be identical ordifferent.

The following are further preferred embodiments within the scope of theinvention:

(3) A compound according to (1) or (2) of the formula I, in which Z₁ isan oxygen atom;

(4) A compound according to any one of (1) to (3) of the formula I, inwhich Z₂ is an oxygen atom;

(5) A compound according to any one of (1) to (4) of the formula I, inwhich R₁ is a phenyl, pyridyl or pyrazolyl group, which is unsubstitutedor preferably substituted;

especially a phenyl, pyridyl or pyrazolyl group, which is substitutedindependently by 1 to 3 substituents, selected from the group,consisting of halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,halo-C₁-C₆alkoxy and a phenyl or pyridyl group, which group isunsubstituted or preferably substituted;

more especially a phenyl, pyridyl or pyrazolyl group, which issubstituted independently by 1 to 3 substituents, selected from thegroup, consisting of halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,halo-C₁-C₆alkoxy and a phenyl or pyridyl group, which group issubstituted independently by 1 to 3 substituents, selected from thegroup, consisting of halogen and C₁-C₆alkyl;

preferably a phenyl or pyridyl group, which is substituted independentlyby 1 to 3 substituents, selected from the group, consisting ofC₁-C₆alkyl and halo-C₁-C₆alkyl; or a pyrazolyl group, which issubstituted independently by 1 to 3 substituents, selected from thegroup, consisting of halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,halo-C₁-C₆alkoxy and a phenyl or pyridyl group, which group issubstituted independently by 1 to 3 substituents, selected from thegroup, consisting of halogen and C₁-C₆alkyl;

more preferably a pyrazolyl group, which is substituted independently by1 to 3 substituents, selected from the group, consisting of halogen,C₁-C₆alkyl, halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy and a phenyl or pyridylgroup, which group is substituted independently by 1 to 3 substituents,selected from the group, consisting of halogen and C₁-C₆alkyl;

especially a pyrazol-3-yl group, which is substituted independently by 1to 3 substituents, selected from the group, consisting of halogen,C₁-C₆alkyl, halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy and a phenyl or pyridylgroup, which group is substituted independently by 1 to 3 substituents,selected from the group, consisting of halogen and C₁-C₆alkyl;

more especially a pyrazol-3-yl group, which is substituted independentlyby 1 to 3 substituents, selected from the group, consisting of halogen,halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy and a phenyl or pyridyl group, whichgroup is substituted independently by 1 to 3 substituents, selected fromthe group, consisting of halogen and C₁-C₆alkyl; preferably apyrazol-3-yl group, which is substituted independently by 1 to 3substituents, selected from the group, consisting of halogen,halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy and a pyridyl group, which group issubstituted independently by 1 to 3 substituents, selected from thegroup, consisting of halogen;

more preferably a pyrazol-3-yl group, which is substituted independentlyby 1 to 3 substituents, selected from the group, consisting of halogen,halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy and a pyrid-2-yl group, which group issubstituted independently by 1 or 2 substituents, selected from thegroup, consisting of halogen;

especially a pyrazol-5-yl group, which is substituted in the 3-positionby halogen, halo-C₁-C₆alkyl or halo-C₁-C₆alkoxy and in the 1-position bya pyrid-2-yl group, which group is substituted independently by 1 or 2substituents, selected from the group, consisting of halogen;

more especially a pyrazol-5-yl group, which is substituted in the3-position by halogen, halo-C₁-C₆alkyl or halo-C₁-C₆alkoxy and in the1-position by a pyrid-2-yl group, which group is substituted in the3-position by halogen;

preferably a pyrazol-5-yl group, which is substituted in the 3-positionby halogen, halo-C₁-C₆alkyl or halo-C₁-C₆alkoxy and in the 1-position bya pyrid-2-yl group, which group is substituted in the 3-position bychlorine or bromine;

more preferably a pyrazol-5-yl group, which is substituted in the3-position by halo-C₁-C₆alkyl and in the 1-position by a pyrid-2-ylgroup, which group is substituted in the 3-position by chlorine orbromine;

most preferably a pyrazol-5-yl group, which is substituted in the3-position by trifluoromethyl and in the 1-position by a pyrid-2-ylgroup, which group is substituted in the 3-position by chlorine orbromine;

(6) A compound according to any one of (1) to (5) of the formula I, inwhich R₂ is hydrogen or C₁-C₆alkyl;

preferably hydrogen;

(7) A compound according to any one of (1) to (6) of the formula I, inwhich R₃ is hydrogen or C₁-C₆alkyl;

preferably hydrogen;

(8) A compound according to any one of (1) to (7) of the formula I, inwhich R₄ is C₁-C₆alkyl; preferably methyl or isopropyl;

(9) A compound according to any one of (1) to (8) of the formula I, inwhich R₅ and R₈, taken together, are a bond;

(10) A compound according to any one of (1) to (9) of the formula I, inwhich R6 and R₇, taken together, are a group of the formula Ib or agroup of the formula Ic;

(11) A compound according to any one of (1) to (10) of the formula I, inwhich the two carbon atoms, shown in the formula I, to which atoms R₆and R₇ are attached, are two ring members of an aromatic ring;

(12) A compound according to any one of (1) to (1 1) of the formula I,in which R₆ and R₇, taken together, form, together with the two carbonatoms, shown in the formula I, to which atoms they are attached, andtogether with R₅ and with R₈, one of the bicyclic ring systems shown inthe formulae T1 to T85, or shown in the formulae T1 to T71, each ofwhich ring systems is substituted by the two substituents—N(R₂)—C(=Z₁)-R₁ and —C(=Z₂)-N(R₃)—R₄;

preferably taken together, form, together with the two carbon atoms,shown in the formula I, to which atoms they are attached, and togetherwith R₅ and with R₈, one of the bicyclic ring systems shown in theformulae T1, T6, T7, T21, T37 and T38, each of which ring systems issubstituted by the two substituents —N(R₂)—C(=Z₁)-R, and—C(=Z₂)-N(R₃)—R₄;

more preferably taken together, form, together with the two carbonatoms, shown in the formula I, to which atoms they are attached, andtogether with R₅ and with R₈, one of the bicyclic ring systems shown inthe formulae T1 and T7, or shown in the formulae T2, T22, T75, T76, T78,T79 and T81, each of which ring systems is substituted by the twosubstituents —N(R₂)—C(=Z₁)-R, and —C(=Z₂)-N(R₃)—R₄.

A further preferred subgroup of the compounds of formula I isrepresented by the compounds of formulae VIIa and VIIb

wherein

R₀₁ is hydrogen; amino or nitro;

R₀₂ is hydrogen or C₁-C₄alkyl;

R₀₃ is C₁-C₄alkyl, C₁-C₄alkyl mono- or disubstituted by cyano, COOH,nitro, C₁-C₄alkoxy or cyclopropyl;

C₂-C₈alkenyl, C₂-C₈alkenyl substituted by halogen;

C₁-C₄alkoxy, C₃-C₆-alkinyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropyl substituted by C₁-C₄alkyl, pyridyl,phenyl-C₂-C₆alkenyl or cyclopropyl;

cyclobutyl substituted by C₁-C₄alkyl;

cyclopentylthio-C₁-C₄alkyl, benzyloxy, benzyloxy substituted by halogen;

benzylthio-C₁-C₄alkyl, wherein the benzyl group may itself besubstituted by C₁-C₄alkyl;

thiophenyl substituted by halophenyl;

phenoxy-C₁-C₄alkyl, wherein the phenyl group may be mono- ordisubstituted by halogen;

phenyl-C₁-C₄alkyl, wherein the phenyl group may itself be mono- ordisubstituted by substituents selected from halogen, nitro,benzothiazol-2-yloxy, C₁-C₄haloalkyl, C₁-C₄alkoxy and C₁-C₄alkyl;

3,4-dihydro-2H-benzo[b][1,4]dioxepinyl, 1,2,3,4-tetrahydro-naphthalenylsubstituted by C₁-C₄alkoxy;

C₂-C₆alkenyloxy, isoxazolyl substituted by C₁-C₄alkyl;

thiazolyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, phenyl substituted byhydroxy, halophenyloxy, C₁-C₄alkyl-silyl(C₁-C₄-alkyl)₃ or C₂-C₆alkinyl;

pyridyl substituted by C₁-C₄alkoxy;

C₁-C₆alkylthio-C₁-C₄alkyl, C₂-C₆alkenylthio-C₁-C₄alkyl,C₃-C₆alkinylthio-C₁-C₄alkyl, dioxolan-2-yl-C₁-C₄alkyl,(C₁-C₄alkyl-dioxolan-2-yl)-C₁-C₄alkyl, triazolyl-C₁-C₄alkyl,thienyl-C₁-C₄alkyl, morpholinyl-C₁-C₄alkyl, C₁-C₄alkylthio-C₁-C₄alkyl,2,3-dihydro-1H-isoindolyl, halo-substituted-thiazolyl-C₁-C₄alkyl,C₁-C₄alkylsulfonyl-C₁-C₄alkyl or quinolylthio-C₁-C₄alkyl, wherein thequinoline group may be substituted by C₁-C₄haloalkyl;

R₀₄ is C₁-C₄haloalkyl;

R₀₅ is halogen;

each of R₀₆ and R₀₁₀, which may be the same or different, representshydrogen, C₁-C₆alkyl, C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonylamino,hydroxy, cyano, halogen or C₁-C₆lkoxy;

R₀₇ is hydrogen, nitro or halogen;

Y₀₁ is C(R₀₈), sulfur, nitrogen or a chemical bond;

R₀₈ is hydrogen, halogen, C₁-C₄alkyl or nitro;

Y₀₂ is C(R₀₉), a chemical bond, or is nitrogen or sulfur; and R₀₉ ishydrogen, phenyl, phenyl substituted by halogen, or halogen.

Preferred compounds of the formula VIIa are those, wherein

R₀₁ is hydrogen; R₀₂ is hydrogen; R₀₃ is C₁-C₄alkyl, preferably methyl;R₀₄ is C₁-C₄fluoroalkyl, preferably trifluoromethyl; R₀₅ is chloro; R₀₆is halogen, preferably chloro; R₀₇ is hydrogen;

R₀₁₀ is hydrogen; Y₀₁ is C(R₀₈); R₀₈ is halogen, preferably chloro; Y₀₂is C(R₀₉), and R₀₉ is hydrogen.

Especially preferred within the scope of the invention are the compoundsof the formula I mentioned in the Examples P3, P6 and P9 to P11.

Individually preferred within the scope of the invention is each of thecompounds T1.1, T1.3, T6.1, T6.3, T7.1, T7.3, T21.3, T37.3 and T38.3.

Also individually preferred within the scope of the invention is each ofthe compounds T2.1, T22.3, T75.1, T75.3, T76.1, T76.3, T78.1, T79.1 andT81.1.

The process according to the invention for preparing compounds of theformula I is carried out analogously to known processes. In the sectionthat follows, the substituents R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, Z₁ and Z₂are as defined under formula I in claim 1 unless otherwise stated.

Compounds of formula A, wherein Z₁ and Z₁ are oxygen and R₁ is hydrogen,may be made from the ring opening of a benzoxazinone of formula B withan amine of formula NHR₃R₄. Such amines are either known or they may bemade analogously to known processes. Benzoxazinones of formula B may bemade from amino acids of formula C by treatment with a carboxylic acidof formula R₁—COOH and a dehydrating reagent such as methanesulfonylchloride (optionally in the presence of a base such as pyridine ortriethylamine). Alternatively benzoxazinones of formula B may beobtained by the treatment of amino acids of formula C with an acidchloride of formula R₁—COCl under basic conditions (for example inpyridine), followed if necessary by a second cyclisation step (which maybe achieved using a dehydrating agent for example acetic anhydride).Acid chlorides of formula R₁—COCl may be made from carboxylic acids offormula R₁—COOH under standard conditions (for example by treatment withthionyl chloride or oxalyl chloride). Carboxylic acids of formulaR₁—COOH are either known compounds or they may be made analogously toknown processes.

Compounds of formula A, wherein Z₁ and Z₁ are sulfur, may be made fromcompounds of formula A, wherein Z₁ and Z₂ are oxygen, by treatment witha thio-transfer reagent such as Lawesson's reagent or phosphoruspentasulfide.

Alternatively, compounds of formula A, wherein Z₁ and Z₁ are oxygen, maybe made by treatment of compounds of formula D, wherein Z₁ is oxygen andR is OH, C₁-C₄alkoxy or Cl, with an amine of formula NHR₃R₄. Thestandard conditions for such acylation reactions are as follows: when Ris OH such reactions are usually carried out in the presence of acoupling reagent such as DCC (N,N′-dicyclohexylcarbodiimide) or EDC(1-Ethyl-3-[3-dimethylamino-propyl]carbodiimide hydrochloride)optionally in the presence of a nucleophilic catalyst such ashydroxybenzotriazole or 4-(dimethylamino)-pyridine. When R is Cl, suchreactions are usually carried out under basic conditions (for example inthe presence of pyridine or triethylamine), again optionally in thepresence of a nucleophilic catalyst. It may be possible to convertesters (wherein R is C₁-C₄alkoxy) directly to amides by heating theester and amine together in a thermal process.

Acid chlorides of formula D, wherein Z₁ is oxygen and R is Cl, may bemade from carboxylic acids of formula D, wherein Z₁ is oxygen and R isOH, under standard conditions (such as treatment with thionyl chlorideor oxalyl chloride). Carboxylic acids of formula D, wherein Z₁ is oxygenand R is OH, may be formed from esters of formula D, wherein Z₁ isoxygen and R is C₁-C₄alkoxy. It is well known for a person skilled inthe art that there are many methods for the hydrolysis of such estersdepending on the nature of the alkoxy group. One widely used method toachieve such a transformation is the treatment of the ester with analkali such as sodium hydroxide in a solvent such as ethanol.

Esters of formula D, wherein Z₁ is oxygen and R is C₁-C₄alkoxy, may bemade by treatment of compounds of formula E, wherein R is C₁-C₄alkoxy,by acylation with compounds of formula

R₁—COOH or R₁—COCl under standard conditions as previously described.Compounds of formula E, wherein R is C₁-C₄alkoxy, may be made fromcompounds of formula C by sequential treatment with an alcohol underacidic conditions and then formation of the N—R₂ bond. It is known to aperson skilled in the art that there are many reported methods for theformation of this bond depending on the nature of the substituent R₂.For example, reductive amination may be achieved by treatment of theamine with an aldehyde or ketone and a reducing agent such as sodiumcyanoborohydride. Alternatively alkylation may be achieved by treatingthe amine with an alkylating agent such as an alkyl halide, optionallyin the presence of a base. Alternatively arylation may be achieved bytreatment of the amine with an aryl halide or sulfonate in the presenceof a suitable catalyst/ligand system, often a palladium (0) complex.

Alternatively, compounds of formula E, wherein R is C₁-C₄alkoxy, may bemade from a compound of formula F, wherein R is C₁-C₄alkoxy and LG is aleaving group such as fluoro, chloro or sulfonate, via nucleophilicdisplacement of the leaving group by an amine of formula R₂—NH₂. Suchcompounds of formula F and amines of formula R₂—NH₂ are either knowncompounds or can be made by known methods obvious to someone skilled inthe art.

Compounds of formula A, wherein Z₁ is sulfur and Z₂ is oxygen, can bemade from compounds of formula D, wherein Z₁ is oxygen and R is OH orC₁-C₄alkoxy, by treatment with a thio-transfer reagent such asLawessen's reagent or phosphorus pentasulfide prior to coupling with theamine of formula NHR₃R₄.

Alternatively, compounds of formula D, wherein R is OH and Z₁ is oxygen,may be dehydrated to benzoxazinones of formula B by treatment with adehydrating agent such as acetic anhydride.

Alternatively, compounds of formula A, wherein Z₁ and Z₂ are oxygen, maybe made by the treatment of compounds of formula G, wherein Z₂ isoxygen, with a carboxylic acid of formula R₁—COOH or an acid chloride offormula R₁—COCl as previously described. Compounds of formula G, whereinZ₂ is oxygen, may be formed from compounds of formula H, wherein P is asuitable protecting group and R is OH, Cl or C₁-C₄alkoxy, by amide bondformation with an amine of formula NHR₂R₃ as previously described forcompounds of formula D, followed by removal of the protecting group Punder standard conditions. Compounds of formula H, wherein R is OH orC₁-C₄alkoxy, may be made by the protection of the amine functionality incompounds of formula E, wherein R is OH or C₁-C₄alkoxy. Suitableprotecting groups include carbamates (such as t-butyloxycarbonyl,allyloxycarbonyl and benzyloxycarbonyl), trialkylsilyl groups (such ast-butyldimethylsilyl) and acyl groups (such as acetyl). The formationand removal of such groups is widely reported in the literature and iswell known to a person skilled in the art.

For compounds of formula H and compounds of formula E, the esters(wherein R is C₁-C₄alkoxy) may be hydrolysed to the acids (wherein R isOH) by treatment with an alkali such as sodium hydroxide in a solventsuch as ethanol. The acids (wherein R is OH) may be converted to theacid chlorides (wherein R is Cl) by treatment with thionyl chloride oroxalyl chloride as previously described for compounds of formula D.

Alternatively, it may be possible to convert compounds of formula E,wherein R is OH, Cl or C₁-C₄alkoxy, directly to compounds of formula Gby amide bond formation with an amine of formula NHR₃R₄ under standardconditions (as previously described for compounds of formula D).

Alternatively, compounds of formula G, wherein Z₂ is oxygen, may be madefrom compounds of formula JK, wherein Z₂ is oxygen and LG is a leavinggroup such as fluoro, chloro or sulfonate, by displacement of theleaving group with a compound of formula R₂NH₂. Such reactions areusually performed under basic conditions. Such compounds of formula JKmay be made from compounds of formula J, wherein R is Cl or OH and LG isa leaving group as previously described, via amide bond formation understandard conditions as previously described. Such compounds of formula Jand formula E are either known compounds or may be made by known methodsby someone skilled in the art.

Compounds of formula A, wherein Z₁ is oxygen and Z₂ is sulfur, may bemade by treatment of compounds of formula JK, wherein Z₂ is oxygen andLG is a leaving group, or compounds of formula G, wherein Z₂2 is oxygen,with a thio-transfer reagent such as Lawesson's reagent or phosphoruspentasulfide prior to elaborating to compounds of formula A, wherein Z₁is oxygen and Z₂ is sulfur, as previously described for compounds offormula A, wherein Z₁ is oxygen and Z₂ is oxygen).

Compounds of formula C are either known or may be made by methods knownto a person skilled in the art. For instance, amino acids of formula Cmay be formed by hydrolysis of isatoic anhydrides of formula K.Alternatively, isatoic anhydrides of formula K may be reacted withamines of formula NHR₃R₄ to give compounds of formula G, wherein R₁ isH, directly. Isatoic anhydrides of formula K are either known compoundsor may be made by known methods obvious to those skilled in the art, forinstance they made be derived from treatment of amino acids of formula Cwith phosgene or a synthetic equivalent of phosgene (for examplecarbonyl diimidazole).

Alternatively, compounds of formula C may be derived from the treatmentof an isatin of formula L with hydrogen peroxide under basic conditions.Isatins of formula L are either known or may be made by methods known topersons skilled in the art, for example they may be derived from aminocompounds of formula M, wherein R₅ and R₈ taken together form anadditional bond between the carbon atoms bearing substituents R₆ and R₇,by treatment for example with oxalyl chloride (optionally in thepresence of a Lewis acid catalyst) or chloral hydrate under variousconditions. Amino compounds of formula M are either known compounds ormay be made by known methods obvious to those skilled in the art.

Alternatively, compounds of formula C, wherein R₅ and R₈ taken togetherform an additional bond between the carbon atoms bearing substituents R₆and R₇, may be derived from the treatment of an isoxazole of formula Nwith aqueous base. Isoxazoles of formula N may be derived fromnitroaldehydes of formula O by treatment with a reducing agent such aszinc in acetic acid. Nitroaldehydes of formula O are either known or maybe made by methods known to persons skilled in the art, for instancethey may be derived from nitro compounds of formula P by treatment withchloroform under basic conditions followed by treatment with strongaqueous acid. Alternatively, nitroaldehydes of formula O may be derivedfrom oxidation of 1-nitro-2-methyl aromatic compounds of formula Q. Aparticularly convenient method of achieving such an oxidation involvestreating the compound Q with dimethylformamide dimethylacetal underbasic conditions followed by treatment with sodium periodate. Compoundsof formula P and Q are either known or may be made by methods known tothose skilled in the art, for instance compounds of formula Q may besynthesised from compounds of formula R by nitration (e.g. with amixture of nitric acid and sulphuric acid).

An alternative synthesis of compounds of formula G, wherein R₂ ishydrogen, may be achieved by the reduction of nitro compounds of formulaS. There are numerous methods for achieving such a transformationreported in the literature such as treatment with tin or iron underacidic conditions, or hydrogenation catalysed by a noble metal such aspalladium on carbon. Compounds of formula S may be derived fromcompounds of formula T, wherein R is OH, Cl, or C₁-C₄alkoxy, viaacylation with an amine of formula NHR₃R₄ under the standard conditionsalready described for a compound of formula D. Similarly conversion ofesters of formula T, wherein R is C₁-C₄alkoxy, to acids of formula T,wherein R is OH, to acid chlorides of formula T, wherein R is Cl, isalso described for compounds of formula D. Compounds of formula T areeither known or may be made by methods known to persons skilled in theart.

It must be recognised that some reagents and reaction conditions may notbe compatible with certain functionalities that may be present in themolecules described. In such cases it may be necessary to employstandard protection/deprotection protocols comprehensively reported inthe literature and well known to a person skilled in the art.

Also in some cases it may be necessary to perform further routinesynthetic steps not described herein to complete the synthesis of thedesired compounds. An artisan will also recognise that it may bepossible to achieve the synthesis of the desired compounds by performingsome of the steps in these synthetic routes in a different order to thatdescribed.

A person skilled in the art will also recognise that it may be possibleto perform standard functional group interconversions or substitutionreactions on the compounds described herein to introduce or modifyexisting substituents.

The reactants can preferably be reacted in the presence of a base.Examples of suitable bases are alkali metal or alkaline earth metalhydroxides, alkali metal or alkaline earth metal hydrides, alkali metalor alkaline earth metal amides, alkali metal or alkaline earth metalalkoxides, alkali metal or alkaline earth metal acetates, alkali metalor alkaline earth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactions are advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between room temperature and approximately +80° C.

The compounds of formula B, D and of formula A, wherein Z₂ is sulfur(compounds of formula AA) and, where appropriate, the tautomers thereof,in each case in free form or in salt form, are novel and are alsosubjects of the invention.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds of formula I, acid addition salts, for example,by treatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl celulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The invention relates to all those embodiments of the process by which,starting from a compound obtainable at any level of the process asstarting material or intermediate, all or some of the missing steps arecarried out or a starting material is used in the form of a derivativeand/or salt and/or racemates or antipodes thereof or, in particular, isformed under the reaction conditions.

Those starting materials and intermediates, in each case in free form orin salt form, which lead to the compounds of formula I or salts thereofwhich have been described at the outset as being particularly valuableare preferably used in the process of the present invention.

In particular, the invention relates to the preparation processesdescribed in the Examples P1 to P11.

Starting materials and intermediates, in each case in free form or saltform, which are used in accordance with the invention for thepreparation of the compounds of formula I or salts thereof and which arenovel, a process for their preparation, and their use as startingmaterials and intermediates for the preparation of the compounds offormula I are also a subject of the invention; in particular, thisapplies to the compounds of formula II, IV and V.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly,i.e. in destruction of the pests, which takes place either immediatelyor only after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,Argas spp., Boophi-lus spp., Brevipalpus spp., Bryobia praetiosa,Calipitrimerus spp., Chorioptes spp., Derma-nyssus gallinae,Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,Oly-gonychus pratensis, Ornithodoros spp., Panonychus spp.,Phyllocoptruta oleivora, Polypha-gotarsonemus latus, Psoroptes spp.,Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp.and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp.,Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrusspp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinusspp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. andTrogoderma spp.;

from the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphoraerythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebraspp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilusspp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoliaspp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletispomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.;

from the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,Eurygaster spp., Lep-tocorisa spp., Nezara spp., Piesma spp., Rhodniusspp., Sahlbergella singularis, Scotino-phara spp. and Triatoma spp.;

from the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,Aphididae, Aphis spp., Aspi-diotus spp., Bemisia tabaci, Ceroplasterspp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccushesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,Macrosiphus spp., Myzus spp., Nephoteftix spp., Nilaparvata spp.,Parlatoria spp., Pemphigus spp., Planococ-cus spp., Pseudaulacaspisspp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideusspp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Triozaerytreae and Unaspis citri;

from the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpiniapolytoma, Hoplo-campa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

Reticulitermes spp.;

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,Carposina nipponensis, Chilo spp., Choristoneura spp., Clysiaambi-guella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaspp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp.,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Gra-pholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis,Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella,Lithocollethis spp., Lobesia botrana, Lymantria spp., Ly-onetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,Pectinophora gossypi-ela, Phthorimaea operculella, Pieris rapae, Pierisspp., Plutella xylostella, Prays spp., Scir-pophaga spp., Sesamia spp.,Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp.,Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Periplaneta spp. and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii,Taeniothrips spp., Thrips palmi and Thrips tabaci; and

from the order Thysanura, for example,

Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops.

The term “crops” is to be understood as including also crops that havebeen rendered tolerant to herbicides like bromoxynil or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, forexample primisulfuron, prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors as a result of conventional methods ofbreeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady®, Herculex I® and LibertyLink®.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). In the case of modifiedtoxins, one or more amino acids of the naturally occurring toxin arereplaced. In such amino acid replacements, preferably non-naturallypresent protease recognition sequences are inserted into the toxin, suchas, for example, in the case of CryIIIA055, a cathepsin-D-recognitionsequence is inserted into a CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Boligard I® (cotton variety that expressesa CryIA(c) toxin); Boligard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);Nature-Gard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIIIA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NU00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Other fields of application of the active ingredients according to theinvention are the protection of stored products and stores and ofmaterial, such as wood, textiles, floor coverings or buildings, and, inthe hygiene sector, particularly the protection of humans, domesticanimals and productive livestock against pests of the abovementionedtype.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymeric substances, which comprise—at least—one ofthe active ingredients according to the invention and which are to beselected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable particulate adsorptive carriersfor granules are porous types, such as pumice, brick grit, sepiolite orbentonite, and suitable non-sorptive carrier materials are calcite orsand. In addition, a large number of granulated materials of inorganicor organic nature can be used, in particular dolomite or comminutedplant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having1 to approximately 10 carbon atoms in the alkyl chain and approximately20 to approximately 250 ethylene glycol ether groups and approximately10 to approximately 100 propylene glycol ether groups. Normally, theabovementioned compounds contain 1 to approximately 5 ethylene glycolunits per propylene glycol unit. Examples which may be mentioned arenonylphenoxypolyethoxyethanol, castor oil polyglycol ether,polypropylene glycol/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethyl-ammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise from 0.0001 to 99.9999%, inparticular 0.1 to 95%, of active ingredient, and 0.0001 to 99.9999%, inparticular 5 to 99.9%, of—at least—one solid or liquid auxiliary, itbeing possible, as a rule, for 0 to 25%, in particular 0.1 to 20%, ofthe compositions to be surfactants (% in each case is per cent byweight). While concentrated compositions are more preferred ascommercially available goods, the end user uses, as a rule, dilutecompositions which have considerably lower concentrations of activeingredient.

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally or acaricidally active ingredients. Suitableadditions to active ingredients here are, for example, representativesof the following classes of active ingredients: organophosphoruscompounds, nitrophenol derivatives, thioureas, juvenile hormones,formamidines, benzophenone derivatives, ureas, pyrrole derivatives,carbamates, pyrethroids, chlorinated hydrocarbons, acylureas,pyridylmethyleneamino derivatives, macrolides, neonicotinoids andBacillus thuringiensis preparations.

Examples of especially suitable mixing partners include compoundsselected from the following group M:

Group M: especially suitable mixing partners for the compounds offormula I: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrinhigh-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos;dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos;kinoprene; lufenuron; methacriphos; methidathion; monocrotophos;phosphamidon; profenofos; diofenolan; a compound obtainable from theBacillus thuringiensis strain GC91 or from strain NCTC11821;pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos;tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl;benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio;cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhalothrin;alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron;endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate;formothion; methiocarb; heptenophos; imidacloprid; thiamethoxam;clothianidin; isoprocarb; methamidophos; methomyl; mevinphos; parathion;parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron;terbufos; triazamate; fenobucarb; tebufenozide; fipronil;beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin;pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid; emamectin;emamectin-benzoate; spinosad; a plant extract that is active againstinsects; a preparation that comprises nematodes and is active againstinsects; a preparation obtainable from Bacillus subtilis; a preparationthat comprises fungi and is active against insects; a preparation thatcomprises viruses and is active against insects; chlorfenapyr; acephate;acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A;azinphos M; azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC;brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben;cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos;chlormephos; cis-resmethrin; clocythrin; clofentezine; cyanophos;cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl;dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos;dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos;etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin;fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate;flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH;hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion;ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb;milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemethonM; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim;pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos; prothoate;pyrachlophos; pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide;salithion; sebufos; sulfotep; suiprofos; tebufenpyrad; tebupirimphos;tefluthrin; temephos; terbam; tetrachlorvinphos; thiacloprid; thiafenox;thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin;triarathene; triazophos; triazuron; trichlorfon; triflumuron;trimethacarb; vamidothion; xylylcarb; YI 5301/5302; zetamethrin;DPX-MP062-indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylylmethylcarbamate); or the fungus pathogen Metarhizium anisopliae.

The following mixtures of the compounds of formula I with one member ofthe group M are preferred (in the following listing, “M” means onemember selected from the group M.)

T1.1+M; T38.3+M; T37.3+M; T20.1+M; T1.3+M; T1.121+M; T2.1+M; T2.3+M;T6.1+M; T6.3+M; T7.1+M; T7.3+M; T21.3+M; T22.3+M; T46.1+M; T46.3+M;T50.1+M; T50.3+M; T51.1+M; T51.3+M; T52.1+M; T52.3+M; T53.1+M; T53.3+M;T72.1+M; T72.3+M; T72.207+M; T72.273+M; T73.1+M; T73.3+M; T73.207+M;T73.273+M; T74.1+M; T74.3+M; T75.1+M; T75.3+M; T76.1+M; T76.3+M;T77.1+M; T77.3+M; T78.1+M; T78.3+M; T79.1+M; T80.3+M; T81.1+M; T81.3+M;T82.1+M; T83.3+M; T84.3+M and T85.3+M; P2.001+M; P2.002+M; P2.003+M;P2.004+M; P2.005+M; P2.006+M; P2.007+M; P2.008+M; P2.009+M; P2.010+M;P2.011+M; P2.012+M; P2.013+M; P2.014+M; P2.015+M; P2.016+M; P2.017+M;P2.018+M; P2.019+M; P2.020+M; P2.021+M; P2.022+M; P2.023+M; P2.024+M;P2.025+M; P2.026+M; P2.027+M; P2.028+M; P2.029+M; P2.030+M; P2.031+M;P2.032+M; P2.033+M; P2.034+M; P2.035+M; P2.036+M; P2.037+M; P2.038+M;P2.039+M; P2.040+M; P2.041+M; P2.042+M; P2.043+M; P2.044+M; P2.045+M;P2.046+M; P2.047+M; P2.048+M; P2.049+M; P2.050+M; P2.051+M; P2.052+M;P2.053+M; P2.054+M; P2.055+M; P2.056+M; P2.057+M; P2.058+M; P2.059+M;P2.060+M; P2.061+M; P2.062+M; P2.063+M; P2.064+M; P2.065+M; P2.066+M;P2.067+M; P2.068+M; P2.069+M; P2.070+M; P2.071+M; P2.072+M; P2.073+M;P2.074+M; P2.075+M; P2.076+M; P2.077+M; P2.078+M; P2.079+M; P2.080+M;P2.081+M; P2.082+M; P2.083+M; P2.084+M; P2.085+M; P2.086+M; P2.087+M;P2.088+M; P2.089+M; P2.090+M; P2.091+M; P2.092+M; P2.093+M; P2.094+M;P2.095+M; P2.096+M; P2.097+M; P2.098+M; P2.099+M; P2.100+M; P2.101+M;P2.102+M; P2.103+M; P2.104+M; P2.105+M; P2.106+M; P2.107+M; P2.108+M;P2.109+M; P2.110+M; P2.111+M; P2.112+M; P2.113+M; P2.114+M; P2.115+M;P2.116+M; P2.117+M; P2.118+M; P2.119+M; P2.120+M; P2.121+M; P2.122+M;P2.123+M; P2.124+M; P2.125+M; P2.126+M; P2.127+M; P2.128+M; P2.129+M;P2.130+M; P2.131+M; P2.132+M; P2.133+M; P2.134+M; P2.135+M; P2.136+M;P2.137+M; P2.138+M; P2.139+M; P2.140+M; P2.141+M; P2.142+M; P2.143+M;P2.144+M; P2.145+M; P2.146+M; P2.147+M; P2.148+M; P2.149+M; P2.150+M;P2.151+M; P2.152+M; P2.153+M; P2.154+M; P2.155+M; P2.156+M; P2.157+M;P2.158+M; P2.159+M; P2.160+M; P2.161+M; P2.162+M; P2.163+M; P2.164+M andP2.165+M.

The compositions can also comprise further solid or liquid auxiliaries,such as stabilizers, for example unepoxidized or epoxidized vegetableoils (for example epoxidized coconut oil, rapeseed oil or soya oil),antifoams, for example silicone oil, preservatives, viscosityregulators, binders and/or tackifiers, fertilizers or other activeingredients for achieving specific effects, for example bactericides,fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds of formula I for the preparation of these compositions arealso a subject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers or kernels, or nursery plants, against pests of theabovementioned type. The propagation material can be treated with thecompositions prior to planting, for example seed can be treated prior tosowing. Alternatively, the compositions can be applied to seed kernels(coating), either by soaking the kernels in a liquid composition or byapplying a layer of a solid composition. It is also possible to applythe compositions when the propagation material is planted to the site ofapplication, for example into the seed furrow during drilling. Thesetreatment methods for plant propagation material and the plantpropagation material thus treated are further subjects of the invention.

The examples which follow are intended to illustrate the invention. Theydo not limit the invention. Temperatures are given in degrees Celsius.The abbreviation “M. P.” means “melting point”.

PREPARATION EXAMPLES Example P1

1.9 g (14.7 mmol) of N-chlorosuccinimide and 10 mg of 2,2′-azoisobutyricnitrile are added to a suspension of 2.5 g (13.3 mmol) of2-amino-3-carboxy-naphthalene in 100 ml of tetrachloromethane. Thereaction mixture is stirred for 18 hours at room temperature, treatedwith 250 ml of aqueous sodium chloride solution and extracted with ethylacetate (3×250 ml): The combined organic layers are dried over magnesiumsulfate and filtered, and the filtrate is concentrated in vacuo. Thisgives the title compound in the form of a brown solid [¹H-NMR (CDCl₃):8.53 (s, 1H), 7.98 (d, 1H), 7.73 (d, 1H), 7.55 (t, 1H), 7.25 (t, 1H)].

Example P2

In a nitrogen atmosphere 0.5 ml (5.75 mmol) of oxalyl chloride are addeddropwise at room temperature with stirring to a suspension of 295 mg(1.0 mmol) of5-carboxy-1-(3-chloropyrid-2-yl)-3-trifluoromethyl-pyrazole in 2 ml ofdichloromethane. The reaction mixture is stirred for 1 hour and thenadded dropwise to a solution of 0.25 g (1 mmol) of the title compound ofExample P1 in a mixture of 20 ml of dichloromethane and 0.38 ml oftriethylamine. The reaction mixture is subsequently stirred for 3 hours.Further 0.7 ml of triethylamine are added, followed by the addition of asingle portion of 0.22 ml (2.8 mmol) of methane sulfonic acid chloride.The reaction mixture is then stirred for 18 hours and concentrated invacuo, and the residue is purified by column chromatography [silica gel;hexane/ethyl acetate (3:1)], which gives the title compound [¹H-NMR(CDCl₃): 8.78 (s, 1H), 8.61 (m, 1H), 8.30 (m, 2H), 8.03 (dd, 1H), 7.78(m, 1H), 7.67 (m, 1H), 7.56 (m, 2H); MS (electrospray): 477, 479, 481((M+H)⁺)].

Example P3

In a nitrogen atmosphere 1 ml of a solution (2.0 M) of methylamine inanhydrous tetrahydrofuran is added with stirring to a solution of 0.07 g(0.15 mmol) of the title compound of Example P2 in 5 ml of anhydroustetrahydrofuran. The reaction mixture is heated to 50° for 1 hour,allowed to cool to room temperature and concentrated in vacuo, and theresidue is purified by column chromatography [silica gel; hexane,followed by hexane/ethyl acetate (3:1)], which gives the title compoundT1.1 [¹H-NMR (DMSO-d₆): 10.80 (s, 1H), 8.53 (d, 1H), 8.45 (br s, 1H),8.21 (m, 2H), 8.08 (m, 2H), 7.87 (s, 1H), 7.78 (t, 1H), 7.70 (t, 1H),7.64 (dd, 1H), 2.70 (d, 3H); MS (electrospray): 508, 510, 512 ((M+H)⁺)].

Example P4

0.91 ml (8.46 mmol) of methyl acetoacetate and 1.98 ml (16.9 mmol) oftin tetrachloride are added to a solution of 1 g (8.46 mmol) of1-amino-2-cyano-benzene in 20 ml of toluene. The reaction mixture isheated to reflux for 2 hours, allowed to cool to room temperature andconcentrated in vacuo. The residue is suspended in 250 ml of aqueoussodium carbonate solution, and the suspension is stirred for 30 minutes,allowed to stand overnight and then extracted with ethyl acetate (3×250ml). The combined organic layers are dried over magnesium sulfate andfiltered, the filtrate is concentrated in vacuo, and the yellow solidresidue is triturated with diethyl ether. This gives the title compoundin the form of a yellow powder [¹H-NMR (CDCl₃): 7.88 (d, 1H), 7.77 (d,1H), 7.68 (m, 1H), 7.43 (m, 1H), 7.06 (br s, 2H), 3.96 (s, 3H), 2.82 (s,3H); MS (electrospray): 217 ((M+H)⁺)].

Example P5

In a nitrogen atmosphere 4 drops of N,N-dimethylformamide and then 0.08ml (0.93 mmol) of oxalyl chloride are added dropwise at room temperaturewith stirring to a suspension of 250 mg (0.86 mmol) of5-carboxy-1-(3-chloropyrid-2-yl)-3-trifluoromethyl-pyrazole in 10 ml ofdichloromethane. The reaction mixture is stirred for 1 hour, the solventis removed in vacuo, and the residue is co-evaporated three times withtoluene and then suspended in 3 ml of toluene to give the suspension“A”. 105 mg (0.858 mmol) of 4-dimethylaminopyridine are added to asuspension of 185 mg (0.858 mmol) of the title compound of Example P4 in3 ml of toluene to give the suspension “B”. The suspension “A” is addedto the suspension “B”, for a complete transfer of the suspension “A”into the reaction flask the vessel containing the suspension “A” beingrinsed out with a small amount of a mixture of toluene and a few dropsof N,N-dimethylformamide. The reaction mixture is heated to reflux for 3hours and then allowed to cool to room temperature. The yellowprecipitate is filtered off and washed with diethyl ether. The filtrateis washed with 10 ml of water, and the water is back-extracted withethyl acetate (2×50 ml). The combined organic layers are dried overmagnesium sulfate and filtered, the filtrate is concentrated in vacuo,and the residue is purified by column chromatography [silica gel;hexane/ethyl acetate (1:2)], which gives the title compound [¹H-NMR(CDCl₃): 8.66 (d, 1H), 8.09 (d, 1H), 8.03 (d, 1H), 7.86 (t, 1H), 7.67(s, 1H), 7.67 (d, 1H), 7.45 (m, 1H), 7.40 (dd, 1H), 3.09 (s, 3H); MS(electrospray): 458 ((M+H)⁺)].

Example P6

0.022 ml (0.262 mmol) of isopropylamine are added with stirring to asuspension of 40 mg (0.087 mmol) of the title compound of Example P5 in1 ml of anhydrous tetrahydrofuran. The reaction mixture is heated to 60°for 90 minutes, allowed to cool to room temperature and concentrated invacuo, and the residue is purified by column chromatography [silica gel;methanol/dichloromethane (1:9)], which gives the title compound T38.3[¹H-NMR (CDCl₃): 11.17 (s, 1H), 8.42 (d, 1H), 8.09 (s, 1H), 7.81 (d,1H), 7.71 (t, 1H), 7.70 (d, 1H), 7.60 (d, 1H), 7.48 (t, 1H), 7.36 (m,1H), 6.31 (d, 1H), 4.23 (m, 1H), 2.30 (s, 3H), 1.16 (d, 6H); MS(electrospray): 517 ((M+H)⁺)].

Example P7

Starting from 1-amino-2-cyano-cyclopent-1-ene, the title compound can beprepared in a manner analogous to the procedure described in Example P4[¹H-NMR (CDCl₃): 5.77 (br s, 2H), 3.90 (s, 3H), 2.97 (m, 2H), 2.70 (m,2H), 2.15 (m, 2H); MS (electrospray): 207 ((M+H)⁺)].

Example P8

In a nitrogen atmosphere 4 drops of N,N-dimethylformamide and then 0.16ml (1.86 mmol) of oxalyl chloride are added dropwise at room temperaturewith stirring to a suspension of 0.5 g (1.72 mmol) of5-carboxy-1-(3-chloropyrid-2-yl)-3-trifluoromethyl-pyrazole in 20 ml ofdichloromethane. The reaction mixture is stirred for 90 minutes, thesolvent is removed in vacuo, and the residue is co-evaporated threetimes with toluene and then dissolved in 10 ml of tetrahydrofuran togive the solution “A”. 0.24 ml (1.72 mmol) of triethylamine are added toa suspension of 195 mg (0.95 mmol) of the title compound of Example P7in 10 ml of tetrahydrofuran to give the suspension “B”. 5 ml of thesolution “A” are added in portions over a period of 30 minutes to thesuspension “B”. The reaction mixture is stirred for 2.5 hours, treatedwith 10 ml of aqueous sodium hydrogen carbonate solution and extractedwith ethyl acetate (2×40 ml). The combined organic layers are dried overmagnesium sulfate and filtered, the filtrate is concentrated in vacuo,and the residue is purified by column chromatography (silica gel; ethylacetate), which gives the title compound [¹H-NMR (CDCl₃): 10.15 (s, 1H),8.49 (d, 1H), 7.92 (d, 1H), 7.45 (m, 1H), 7.22 (s, 1H), 3.96 (s, 3H),2.99 (m, 2H), 2.75 (m, 2H), 2.67 (s, 3H), 2.06 (m, 2H); MS(electrospray): 480 ((M+H)⁺)].

Example P9

0.04 ml (0.47 mmol) of isopropylamine are added at room temperature withstirring to a mixture of 0.24 ml of a solution (2.0 M) oftrimethylaluminium in hexane and 3 ml of dichloromethane. The reactionmixture is stirred for 40 minutes. A solution of 110 mg (0.22 mmol) ofthe title compound of Example P8 in 3 ml of dichloromethane is added,and the reaction mixture is heated to reflux for 6 hours, allowed tocool to room temperature and to stand overnight and then poured into 20ml of water. The mixture is extracted with dichloromethane (2×30 ml).The combined organic layers are dried over magnesium sulfate andfiltered, the filtrate is concentrated in vacuo, and the residue ispurified by column chromatography [silica gel; ethyl acetate/hexane(2:1), followed by neat ethyl acetate], which gives the title compoundT37.3 [¹H-NMR (CDCl₃): 10.69 (s, 1H), 8.49 (d, 1H), 7.88 (d, 1H), 7.70(s, 1H), 7.42 (m, 1H), 5.89 (d, 1H), 4.24 (m, 1H), 2.87 (t, 2H), 2.57(t, 2H), 2.49 (s, 3H), 2.02 (m, 2H), 1.19 (d, 6H); MS (electrospray):507 ((M+H)⁺)].

Example P10

The compounds listed in the Table P1 and P2 can be prepared in a manneranalogous to the procedures described in the Examples P1 to P9. Meltingpoints are given in ° C. In the following structures, tertiary hydrogenatoms attached to carbon atoms are not drawn, e.g. the group

TABLE P1 Compound Structure MS ¹H-NMR M. P. T1.3

Electrospray: 536, 538, 540 ((M + H)⁺). CDCl₃: 8.43 (d, 1 H), 7.91 (s, 1H), 7.81 (d, 1 H), 7.64 (s,1 H), 7.59 (t, 2 H), 7.33 (m, 2 H), 7.22 (m,1 H), 6.19 (d, 1 H), 4.19 (m, 1 H), 1.18 (d, 6 H). T1.121

Electrospray: 522, 524, 526 ((M + H)⁺). CDCl₃: 10.95 (s, 1 H), 8.43 (dd,1 H), 8.01 (s, 1 H), 7.82 (d, 1 H), 7.64 (d, 1 H), 7.52 (s, 1 H), 7.35(m, 3 H), 7.16 (t, 1 H), 2.77 (s, 3 H), 2.71 (s, 3 H). T2.1

Electrospray: 584, 586, 588, 590 ((M − H)⁺). DMSO-d₆: 10.82 (s, 1 H),8.52 (dd, 1 H), 8.47 (d, 1 H), 8.40 (d, 1 H), 8.20 (d, 1 H), 8.14 (d, 1H), 8.05 (s, 1 H), 7.89 (m, 1 H), 7.87 (s, 1 H), 7.64 (dd, 1 H), 2.69(d, 3 H). T2.3

Electrospray: 614, 616, 618 ((M + H)⁺). DMSO-d₆: 10.80 (s, 1 H), 8.50(dd, 1 H), 8.42 (d, 1 H), 8.32 (d, 1 H), 8.19 (d, 1 H), 8.14 (d, 1 H),8.01 (s, 1 H), 7.89 (s, 1 H), 7.88 (m, 1 H), 7.63 (dd, 1 H), 3.92 (m, 1H),1.06 (d, 6 H). T6.1

Electrospray: 474, 476 ((M + H)⁺). DMSO-d₆: 12.75 (s, 1 H), 9.13 (d, 1H), 8.69 (s, 1 H), 8.60 (d, 1 H), 8.44 (s, 1 H), 8.31 (d, 1 H), 7.91 (m,2 H), 7.74 (dd, 1 H), 7.55 (m, 3 H), 2.89 (d, 3 H). T6.3

Electrospray: 502, 504 ((M + H)⁺). DMSO-d₆: 12.55 (s, 1 H), 8.90 (d, 1H), 8.62 (s, 1 H), 8.59 (d, 1 H), 8.43 (s, 1 H), 8.31 (d, 1 H), 7.94 (d,1 H), 7.90 (d, 1 H), 7.73 (dd, 1 H), 7.55 (m, 3 H), 4.21 (m, 1 H), 1.23(d, 6 H). T7.1

Electrospray: 552, 554, 556 ((M + H)⁺). DMSO-d₆: 10.80 (s, 1 H), 8.52(d, 1 H), 8.42 (s, 1 H), 8.20 (m, 2 H), 8.11 (s, 1 H), 8.05 (d, 1 H),7.88 (s, 1 H), 7.75 (t, 1 H), 7.64 (m, 2 H), 2.70 (d, 3 H). T7.3

Electrospray: 580, 582, 584 ((M + H)⁺). CDCl₃: 10.65 (s, 1 H), 8.43 (d,1 H), 7.98 (s, 1 H), 7.81 (d, 1 H), 7.71 (s, 1 H), 7.60 (d, 1 H), 7.56(d, 1 H), 7.34 (m, 2 H), 7.21 (t, 1 H), 6.12 (d, 1 H),4.20 (m,1 H),1.17(d, 6 H). T21.3

Electrospray: 502, 504 ((M + H)⁺). CDCl₃: 10.97 (s, 1 H), 8.46 (d, 1 H),7.84 (m, 2 H), 7.75 (s, 1 H), 7.72 (m, 1 H), 7.49 (m, 2 H), 7.37 (m, 2H), 7.11 (d, 1 H), 6.15 (d, 1 H), 4.23 (m, 1 H), 1.19 (d, 6 H). T22.3

Electrospray: 536, 538 ((M + H)⁺). CDCl₃: 11.00 (s, 1 H), 8.43 (d, 1 H),7.96 (d, 1 H), 7.87 (s, 1 H), 7.81 (m, 2 H), 7.58 (m, 2 H), 7.36 (m, 1H), 7.05 (s, 1 H), 6.12 (d, 1 H), 4.20 (m, 1 H), 1.20 (d, 6 H). T46.1

261-263 T46.3

246-248 T50.1

145-147 T50.3

143-145 T51.1

165-168 T51.3

146-148 T52.1

211-213 T52.3

269-270 T53.1

183-185 T53.3

259-260 T72.1

226-228 T72.3

229-232 T72.207

230-233 T72.273

184-186 T73.1

205-207 T73.3

223-225 T73.207

192-194 T73.273

Electrospray: 580 ((M + H)⁺). T74.1

133-135 T74.3

206-207 T75.1

Electrospray: 489 ((M + H)⁺). CDCl₃: 11.97 (s, 1 H), 8.50 (br s, 1 H),8.49 (dd, 1 H), 8.00 (d, 1 H), 7.87 (dd, 1 H), 7.69 (m, 1 H), 7.61 (m, 1H), 7.45 (s, 1 H), 7.41 (m, 1 H), 3.09 (d, 3 H), 2.52 (s, 3 H). T75.3

Electrospray: 517 ((M + H)⁺). CDCl₃: 12.06 (s, 1 H), 8.49 (dd, 1 H),8.33 (m, 1 H), 8.04 (d, 1 H), 7.99 (d, 1 H), 7.87 (dd, 1 H), 7.69 (m, 1H), 7.61 (m, 1 H), 7.44 (s, 1 H), 7.41 (m, 1 H), 4.30 (m, 1 H), 2.52 (s,3 H), 1.35 (d, 6 H). T76.1

CDCl₃: 8.47 (d, 1 H), 8.17 (s, 1 H), 8.13 (d, 1 H), 8.08 (m, 1 H), 7.94(d, 1 H), 7.85 (d, 1 H), 7.73 (s, 1 H), 7.67 (m, 1 H), 7.48 (m, 1 H),2.93 (d, 3 H). T76.3

Electrospray: 581 ((M + H)⁺). CDCl₃: 10.95 (s, 1 H), 8.59 (d, 1 H), 8.47(dd, 1 H), 8.39 (s, 1 H), 8.33 (d, 1 H), 8.30 (d, 1 H), 8.04 (d, 1 H),7.89 (s, 1 H), 7.84 (m, 1 H), 7.56 (m, 1 H), 4.02 (m, 1 H), 1.11 (d, 6H). T77.1

Electrospray: 600 ((M + H)⁺). CDCl₃: 10.29 (s, 1 H), 8.47 (dd, 1 H),7.85 (dd, 1 H), 7.81 (s, 1 H), 7.71 (s, 1 H), 7.70 (d, 1 H), 7.63 (d, 1H), 7.40 (m, 1 H), 7.38 (m, 1 H), 7.33 (m, 1 H), 6.26 (m, 1 H), 2.96 (d,3 H). T77.3

Electrospray: 628 ((M + H)⁺). CDCl₃: 10.61 (s, 1 H), 8.45 (dd, 1 H),7.93 (s, 1 H), 7.83 (dd, 1 H), 7.78 (s, 1 H), 7.57 (d, 1 H), 7.36 (m, 2H), 7.24 (m, 1 H), 6.10 (d, 1 H), 4.20 (m, 1 H), 1.16 (d, 6 H). T78.1

Electrospray: 519 ((M + H)⁺). CDCl₃: 10.82 (br s, 1 H), 8.50 (d, 1 H),8.05 (s, 1 H), 7.93 (d, 1 H), 7.84 (d, 1 H), 7.79 (d, 1 H), 7.65 (m, 1H), 7.52 (m, 1 H), 7.45 (m, 1 H), 7.28 (s, 1 H), 6.58 (br s, 1 H), 2.98(d, 3 H). T78.3

Electrospray: 547 ((M + H)⁺). CDCl₃: 11.02 (br s, 1 H), 8.47 (d, 1 H),8.07 (s, 1 H), 7.88 (d, 1 H), 7.82 (d, 1 H), 7.73 (d, 1 H), 7.59 (m, 1H), 7.53 (m, 1 H), 7.48 (s, 1 H), 7.40 (m, 1 H), 6.20 (br s, 1 H), 4.27(m, 1 H) 1.27 (d, 6 H). T79.1

Electrospray: 514 ((M + H)⁺). CDCl₃: 9.15 (s, 1 H), 8.53 (dd, 1 H), 8.22(dd, 1 H), 8.14 (d, 1 H), 8.04 (d, 1 H), 7.83 (s, 1 H), 7.66 (m, 1 H),7.47 (m, 2 H), 2.77 (s, 3 H). T80.3

Electrospray: 503, 505 ((M + H)⁺). CDCl₃: 10.10 (s, 1 H), 8.87 (d, 1 H),8.43 (d, 1 H), 8.09 (d, 1 H), 7.85 (d, 1 H), 7.58 (m, 2 H), 7.49 (m, 2H), 7.38 (m, 1 H), 6.01 (d, 1 H), 4.17 (m, 1 H),1.14 (d, 6 H). T81.1

Electrospray: 489 ((M + H)⁺). CDCl₃: 10.20 (s, 1 H), 8.46 (d, 1 H), 7.94(d, 1 H), 7.87 (d, 1 H), 7.84 (s, 1 H), 7.76 (t, 1 H), 7.74 (d, 1 H),7.55 (t, 1 H), 7.41 (m, 1 H), 6.45 (m, 1 H), 3.04 (d, 3 H), 1.94 (s, 3H). T81.3

Electrospray: 517 ((M + H)⁺). CDCl₃: 10.49 (s, 1 H), 8.44 (d, 1 H), 7.93(d, 1 H), 7.92 (s, 1 H), 7.85 (d, 1 H), 7.75 (t, 1 H), 7.74 (d, 1 H),7.54 (t, 1 H), 7.39 (m, 1 H), 6.29 (d, 1 H), 4.28 (m, 1 H), 1.81 (s, 3H), 1.18 (d, 6 H). T82.1

Electrospray: 463 ((M + H)⁺). DMSO-d₆: 11.58 (s, 1 H), 10.65 (s, 1 H),8.57 (dd, 1 H), 8.26 (dd, 1 H), 7.87 (s, 1 H), 7.84 (m, 1 H), 7.68 (m, 1H), 7.44 (d, 1 H), 7.40 (d, 1 H), 7.21 (t, 1 H) 7.03 (t,1 H), 2.82 (s, 3H). T83.3

Electrospray: 503, 505 ((M + H)⁺). CDCl₃: 11.22 (s, 1 H), 8.90 (m, 1 H),8.44 (d, 1 H), 8.14 (d, 1 H), 7.85 (d, 1 H), 7.78 (s, 1 H), 7.54 (d, 1H), 7.40 (m, 2 H), 7.30 (d, 1 H), 6.22 (d, 1 H), 4.25 (m, 1 H), 1.22 (d,6 H). T84.3

Electrospray: 496, 498 ((M + H)⁺). DMSO-d₆: 13.48 (s, 1 H), 8.54 (d, 1H), 8.10 (d, 1 H), 8.02 (m, 2 H), 7.56 (m, 1 H), 7.46 (s, 1 H), 7.29 (s,1 H), 6.00 (s, 2 H), 4.28 (m, 1 H), 1.26 (d, 6 H). T85.3

220-224 T88.3

261-263 T88.1

264-266 T89.1

274-276 T90.1

242-244 T90.3

256-258 T91.1

265-267 T91.3

251-253

TABLE P2 Phys. Data (MS., NMR, Comp. Nr. Structure M. P in ° C.) P2.001

524 (M + H)+) P2.002

532 ((M + H)+) P2.003

538 ((M + H)+) P2.004

547 ((M + H)+) P2.005

548 ((M + H)+) P2.006

550 ((M + H)+) P2.007

560 ((M + H)+) P2.008

562 ((M + H)+) P2.009

562 ((M + H)+) P2.010

562 ((M + H)+) P2.011

562 ((M + H)+) P2.012

566 ((M + H)+) P2.013

566 ((M + H)+) P2.014

566 ((M + H)+) P2.015

568 ((M + H)+) P2.016

574 ((M + H)+) P2.017

575 ((M + H)+) P2.018

576 ((M + H)+) P2.019

576 ((M + H)+) P2.020

577 ((M + H)+) P2.021

580 ((M + H)+) P2.022

586 ((M + H)+) P2.023

592 ((M + H)+) P2.024

594 ((M + H)+) P2.025

594 ((M + H)+) P2.026

594 ((M + H)+) P2.027

594 ((M + H)+) P2.028

596 ((M + H)+) P2.029

596 ((M + H)+) P2.030 (T1.273)

596 ((M + H)+) P2.031

600 ((M + H)+) P2.032

601 ((M + H)+) P2.033

603 ((M + H)+) P2.034

604 ((M + H)+) P2.035

604 ((M + H)+) P2.036

607 ((M + H)+) P2.037

607 ((M + H)+) P2.038

608 ((M + H)+) P2.039

608 ((M + H)+) P2.040

609 ((M + H)+) P2.041

610 ((M + H)+) P2.042

610 ((M + H)+) P2.043

610 ((M + H)+) P2.044

610 ((M + H)+) P2.045

611 ((M + H)+) P2.046

611 ((M + H)+) P2.047

614 ((M + H)+) P2.048

616 ((M + H)+) P2.049

616 ((M + H)+) P2.050

618 ((M + H)+) P2.051

622 ((M + H)+) P2.052

622 ((M + H)+) P2.053

624 ((M + H)+) P2.054

625 ((M + H)+) P2.055

628 ((M + H)+) P2.056

629 ((M + H)+) P2.057

630 ((M + H)+) P2.058

636 ((M + H)+) P2.059

642 ((M + H)+) P2.060

644 ((M + H)+) P2.061

646 ((M + H)+) P2.062

654 ((M + H)+) P2.063

658 ((M + H)+) P2.064

664 ((M + H)+) P2.065

670 ((M + H)+) P2.066

676 ((M + H)+) P2.067

680 ((M + H)+) P2.068

684 ((M + H)+) P2.069

686 ((M + H)+) P2.070

690 ((M + H)+) P2.071

695 ((M + H)+) P2.072

699 ((M + H)+) P2.073

730 ((M + H)+) P2.074

747 ((M + H)+) P2.075

749 ((M + H)+) P2.076 (T85.273)

459 ((M + H)+) oil P2.077 (T8.1)

488 ((M + H)+) P2.078

507 ((M + H)+) P2.079

522 ((M + H)+) P2.080

524 ((M + H)+) P2.081 (T5.1)

533 ((M + H)+) P2.082

535 ((M + H)+) P2.083

538 ((M + H)+) P2.084 (T20.1)

544 ((M + H)+) P2.085 (T5.207)

559 ((M + H)+) P2.086 (T5.3)

561 ((M + H)+) P2.087 (T20.207)

568 ((M + H)+) P2.088 (T20.3)

570 ((M + H)+) P2.089

581 ((M + H)+) P2.090

582 ((M + H)+) P2.091

593 ((M + H)+) P2.092 (T2.2)

602 ((M + H)+) P2.093 (T2.207)

612 ((M − 1)−) P2.094

612 ((M + H)+) P2.095

614 ((M − 1)−) P2.096

614 ((M + H)+) P2.097

627 ((M + H)+) P2.098

628 ((M + H)+) P2.099

628 ((M − 1)−) P2.100

628 ((M + H)+) P2.101

628 ((M + H)+) P2.102

630 ((M + H)+) P2.103

630 ((M + H)+) P2.104 (T9.1)

632 ((M + H)+) P2.105

632 ((M + H)+) P2.106

642 ((M + H)+) P2.107

646 ((M + H)+) P2.108

646 ((M + H)+) P2.109 (T9.2)

646 ((M + H)+) P2.110

648 ((M + H)+) P2.111

656 ((M + H)+) P2.112 (T9.207)

656 ((M + H)+) P2.113

656 ((M + H)+) P2.114 (T9.3)

660 ((M + H)+) P2.115

670 ((M + H)+) P2.116

670 ((M + H)+) P2.117

671 ((M + H)+) P2.118

672 ((M + H)+) P2.119 (T9.145)

672 ((M − 1)−) P2.120

674 ((M + H)+) P2.121

674 ((M + H)+) P2.122

676 ((M + H)+) P2.123

686 ((M + H)+) P2.124

688 ((M + H)+) P2.125

690 ((M + H)+) P2.126

692 ((M + H)+) P2.127

0.82-086 (t, 3 H), 1.37-1.46 (m, 2 H), 3.07- 3.12 (m, 2 H), 7.64-7.66(m, 1 H), 7.87-7.89 (dd, 1 H), 7.88 (s, 1 H), 8.07 (s, 1 H), 8.13- 8.15(d, 1 H), 8.19-8.21 (d, 1 H), 8.41-8.42 (d, 1 H), 8.48 (br, 1 H), 8.51-8.52 (d, 1 H) P2.128

1.07-7.08 (d, 6 H), 3.90-3.97 (m, 1 H), 6.10 (br s, 2 H), 6.79-6.80 (d,1 H) 7.33-7.35 (d, 1 H), 7.39- 7.43 (m, 1 H), 7.63-7.66 (m, 1 H), 7.88(s, 1 H), 8.00-8.02 (d, 1 H), 8.19 (s, 1 H0, 8.19- 8.21 (d, 1 H),8.51-8.52 (d, 1 H), 10.67 (s, 1 H) P2.129 (T85.3)

220-224° C. P2.130

503 ((M + H)+) P2.131 (T84.3)

496 ((M + H)+) P2.132

517 ((M + H)+) P2.133

658 ((M + H)+) P2.134

630 ((M + H)+) P2.135

611 ((M + H)+) P2.136 (T50.1)

145-147° C. P2.137 (T50.3)

143-145° C. P2.138 (T51.3)

146-148° C. P2.139 (T51.1)

165-168° C. P2.140 (T46.1)

261-263° C. P2.141 (T46.1)

246-248° C. P2.142 (T53.3)

259-260° C. P2.143 (T53.1)

183-185° C. P2.144 (T52.3)

269-270° C. P2.145 (T52.1)

211-213° C. P2.146 (T74.3)

206-207° C. P2.147 (T74.1)

133-135° C. P2.148

212-215° C. P2.149

253-255° C. P2.150

284-286° C. P2.151

273-275° C. P2.152

255-257° C. P2.153

274-276° C. P2.154

255-257° C. P2.155

267-270° C. P2.156

265-267° C. P2.157 (T57.1)

257-259° C. P2.158

253-255° C. P2.159

274-276° C. P2.160 (T57.3)

265-267° C. P2.161

265-267° C. P2.162

254-255° C. P2.163

272-274° C. P2.164

234-236° C. P2.165

284-286° C.

Example P11

The other compounds listed in the Tables 1 to 85 can also be prepared ina manner analogous to the procedures described in the Examples P1 toP10.

The Table A discloses 338 meanings of the variables Z₁, Z₂, R₁, R₂, R₃and R₄ in a compound of the formula 1. TABLE A (I)

Line Z₁ Z₂ —R₁ R₂ R₃ R₄ A.1 O O

H H CH₃ A.2 O O

H H CH₂CH₃ A.3 O O

H H CH(CH₃)₂ A.4 O O

H H CH₃ A.5 O O

H H CH₂CH₃ A.6 O O

H H CH(CH₃)₂ A.7 O O

H H CH₃ A.8 O O

H H CH₂CH₃ A.9 O O

H H CH(CH₃)₂ A.10 O O

H H CH₃ A.11 O O

H H CH₂CH₃ A.12 O O

H H CH(CH₃)₂ A.13 O O

H H CH₃ A.14 O O

H H CH₂CH₃ A.15 O O

H H CH(CH₃)₂ A.16 O O

H H CH₃ A.17 O O

H H CH₂CH₃ A.18 O O

H H CH(CH₃)₂ A.19 O O

H H CH₃ A.20 O O

H H CH₂CH₃ A.21 O O

H H CH(CH₃)₂ A.22 O O

H H CH₃ A.23 O O

H H CH₂CH₃ A.24 O O

H H CH(CH₃)₂ A.25 S S

H H CH₃ A.26 S S

H H CH₂CH₃ A.27 S S

H H CH(CH₃)₂ A.28 S S

H H CH₃ A.29 S S

H H CH₂CH₃ A.30 S S

H H CH(CH₃)₂ A.31 S S

H H CH₃ A.32 S S

H H CH₂CH₃ A.33 S S

H H CH(CH₃)₂ A.34 S S

H H CH₃ A.35 S S

H H CH₂CH₃ A.36 S S

H H CH(CH₃)₂ A.37 S S

H H CH₃ A.38 S S

H H CH₂CH₃ A.39 S S

H H CH(CH₃)₂ A.40 S S

H H CH₃ A.41 S S

H H CH₂CH₃ A.42 S S

H H CH(CH₃)₂ A.43 S S

H H CH₃ A.44 S S

H H CH₂CH₃ A.45 S S

H H CH(CH₃)₂ A.46 S S

H H CH₃ A.47 S S

H H CH₂CH₃ A.48 S S

H H CH(CH₃)₂ A.49 O S

H H CH₃ A.50 O S

H H CH₂CH₃ A.51 O S

H H CH(CH₃)₂ A.52 O S

H H CH₃ A.53 O S

H H CH₂CH₃ A.54 O S

H H CH(CH₃)₂ A.55 O S

H H CH₃ A.56 O S

H H CH₂CH₃ A.57 O S

H H CH(CH₃)₂ A.58 O S

H H CH₃ A.59 O S

H H CH₂CH₃ A.60 O S

H H CH(CH₃)₂ A.61 O S

H H CH₃ A.62 O S

H H CH₂CH₃ A.63 O S

H H CH(CH₃)₂ A.64 O S

H H CH₃ A.65 O S

H H CH₂CH₃ A.66 O S

H H CH(CH₃)₂ A.67 O S

H H CH₃ A.68 O S

H H CH₂CH₃ A.69 O S

H H CH(CH₃)₂ A.70 O S

H H CH₃ A.71 O S

H H CH₂CH₃ A.72 O S

H H CH(CH₃)₂ A.73 S O

H H CH₃ A.74 S O

H H CH₂CH₃ A.75 S O

H H CH(CH₃)₂ A.76 S O

H H CH₃ A.77 S O

H H CH₂CH₃ A.78 S O

H H CH(CH₃)₂ A.79 S O

H H CH₃ A.80 S O

H H CH₂CH₃ A.81 S O

H H CH(CH₃)₂ A.82 S O

H H CH₃ A.83 S O

H H CH₂CH₃ A.84 S O

H H CH(CH₃)₂ A.85 S O

H H CH₃ A.86 S O

H H CH₂CH₃ A.87 S O

H H CH(CH₃)₂ A.88 S O

H H CH₃ A.89 S O

H H CH₂CH₃ A.90 S O

H H CH(CH₃)₂ A.91 S O

H H CH₃ A.92 S O

H H CH₂CH₃ A.93 S O

H H CH(CH₃)₂ A.94 S O

H H CH₃ A.95 S O

H H CH₂CH₃ A.96 S O

H H CH(CH₃)₂ A.97 O O

CH₃ H CH₃ A.98 O O

CH₃ H CH₂CH₃ A.99 O O

CH₃ H CH(CH₃)₂ A.100 O O

CH₃ H CH₃ A.101 O O

CH₃ H CH₂CH₃ A.102 O O

CH₃ H CH(CH₃)₂ A.103 O O

CH₃ H CH₃ A.104 O O

CH₃ H CH₂CH₃ A.105 O O

CH₃ H CH(CH₃)₂ A.106 O O

CH₃ H CH₃ A.107 O O

CH₃ H CH₂CH₃ A.108 O O

CH₃ H CH(CH₃)₂ A.109 O O

CH₃ H CH₃ A.110 O O

CH₃ H CH₂CH₃ A.111 O O

CH₃ H CH(CH₃)₂ A.112 O O

CH₃ H CH₃ A.113 O O

CH₃ H CH₂CH₃ A.114 O O

CH₃ H CH(CH₃)₂ A.115 O O

CH₃ H CH₃ A.116 O O

CH₃ H CH₂CH₃ A.117 O O

CH₃ H CH(CH₃)₂ A.118 O O

CH₃ H CH₃ A.119 O O

CH₃ H CH₂CH₃ A.120 O O

CH₃ H CH(CH₃)₂ A.121 O O

H CH₃ CH₃ A.122 O O

H CH₃ CH₂CH₃ A.123 O O

H CH₃ CH(CH₃)₂ A.124 O O

H CH₃ CH₃ A.125 O O

H CH₃ CH₂CH₃ A.126 O O

H CH₃ CH(CH₃)₂ A.127 O O

H CH₃ CH₃ A.128 O O

H CH₃ CH₂CH₃ A.129 O O

H CH₃ CH(CH₃)₂ A.130 O O

H CH₃ CH₃ A.131 O O

H CH₃ CH₂CH₃ A.132 O O

H CH₃ CH(CH₃)₂ A.133 O O

H CH₃ CH₃ A.134 O O

H CH₃ CH₂CH₃ A.135 O O

H CH₃ CH(CH₃)₂ A.136 O O

H CH₃ CH₃ A.137 O O

H CH₃ CH₂CH₃ A.138 O O

H CH₃ CH(CH₃)₂ A.139 O O

H CH₃ CH₃ A.140 O O

H CH₃ CH₂CH₃ A.141 O O

H CH₃ CH(CH₃)₂ A.142 O O

H CH₃ CH₃ A.143 O O

H CH₃ CH₂CH₃ A.144 O O

H CH₃ CH(CH₃)₂ A.145 O O

H H C(CH₃)₃ A.146 O O

H H C(CH₃)₃ A.147 O O

H H C(CH₃)₃ A.148 O O

H H C(CH₃)₃ A.149 O O

H H C(CH₃)₃ A.150 O O

H H C(CH₃)₃ A.151 O O

H H C(CH₃)₃ A.152 O O

H H C(CH₃)₃ A.153 O O

H H CH₃ A.154 O O

H H CH₂CH₃ A.155 O O

H H CH(CH₃)₂ A.156 O O

H H CH₃ A.157 O O

H H CH₂CH₃ A.158 O O

H H CH(CH₃)₂ A.159 O O

H H CH₃ A.160 O O

H H CH₂CH₃ A.161 O O

H H CH(CH₃)₂ A.162 O O

H H CH₃ A.163 O O

H H CH₂CH₃ A.164 O O

H H CH(CH₃)₂ A.165 O O

H H CH₃ A.166 O O

H H CH₂CH₃ A.167 O O

H H CH(CH₃)₂ A.168 O O

H H CH₃ A.169 O O

H H CH₂CH₃ A.170 O O

H H CH(CH₃)₂ A.171 O O

H H CH₃ A.172 O O

H H CH₂CH₃ A.173 O O

H H CH(CH₃)₂ A.174 O O

H H CH₃ A.175 O O

H H CH₂CH₃ A.176 O O

H H CH(CH₃)₂ A.177 O O

H H CH₃ A.178 O O

H H CH₂CH₃ A.179 O O

H H CH(CH₃)₂ A.180 O O

H H CH₃ A.181 O O

H H CH₂CH₃ A.182 O O

H H CH(CH₃)₂ A.183 O O

H H CH₃ A.184 O O

H H CH₂CH₃ A.185 O O

H H CH(CH₃)₂ A.186 O O

H H CH₃ A.187 O O

H H CH₂CH₃ A.188 O O

H H CH(CH₃)₂ A.189 O O

H H CH₃ A.190 O O

H H CH₂CH₃ A.191 O O

H H CH(CH₃)₂ A.192 O O

H H CH₃ A.193 O O

H H CH₂CH₃ A.194 O O

H H CH(CH₃)₂ A.195 O O

H H CH₃ A.196 O O

H H CH₂CH₃ A.197 O O

H H CH(CH₃)₂ A.198 O O

H H CH₃ A.199 O O

H H CH₂CH₃ A.200 O O

H H CH(CH₃)₂ A.201 O O

H H CH₃ A.202 O O

H H CH₂CH₃ A.203 O O

H H CH(CH₃)₂ A.204 O O

H H CH₃ A.205 O O

H H CH₂CH₃ A.206 O O

H H CH(CH₃)₂ A.207 O O

H H Cyclopropyl A.208 O O

H H Cyclopropyl A.209 O O

H H Cyclopropyl A.210 O O

H H Cyclopropyl A.211 O O

H H Cyclopropyl A.212 O O

H H Cyclopropyl A.213 O O

H H Cyclopropyl A.214 O O

H H Cyclopropyl A.215 S S

H H Cyclopropyl A.216 S S

H H Cyclopropyl A.217 S S

H H Cyclopropyl A.218 S S

H H Cyclopropyl A.219 S S

H H Cyclopropyl A.220 S S

H H Cyclopropyl A.221 S S

H H Cyclopropyl A.222 S S

H H Cyclopropyl A.223 O S

H H Cyclopropyl A.224 O S

H H Cyclopropyl A.225 O S

H H Cyclopropyl A.226 O S

H H Cyclopropyl A.227 O S

H H Cyclopropyl A.228 O S

H H Cyclopropyl A.229 O S

H H Cyclopropyl A.230 O S

H H Cyclopropyl A.231 S O

H H Cyclopropyl A.232 S O

H H Cyclopropyl A.233 S O

H H Cyclopropyl A.234 S O

H H Cyclopropyl A.235 S O

H H Cyclopropyl A.236 S O

H H Cyclopropyl A.237 S O

H H Cyclopropyl A.238 S O

H H Cyclopropyl A.239 O O

CH₃ H Cyclopropyl A.240 O O

CH₃ H Cyclopropyl A.241 O O

CH₃ H Cyclopropyl A.242 O O

CH₃ H Cyclopropyl A.243 O O

CH₃ H Cyclopropyl A.244 O O

CH₃ H Cyclopropyl A.245 O O

CH₃ H Cyclopropyl A.246 O O

CH₃ H Cyclopropyl A.247 O O

H CH₃ Cyclopropyl A.248 O O

H CH₃ Cyclopropyl A.249 O O

H CH₃ Cyclopropyl A.250 O O

H CH₃ Cyclopropyl A.251 O O

H CH₃ Cyclopropyl A.252 O O

H CH₃ Cyclopropyl A.253 O O

H CH₃ Cyclopropyl A.254 O O

H CH₃ Cyclopropyl A.255 O O

H H Cyclopropyl A.256 O O

H H Cyclopropyl A.257 O O

H H Cyclopropyl A.258 O O

H H Cyclopropyl A.259 O O

H H Cyclopropyl A.260 O O

H H Cyclopropyl A.261 O O

H H Cyclopropyl A.262 O O

H H Cyclopropyl A.263 O O

H H Cyclopropyl A.264 O O

H H Cyclopropyl A.265 O O

H H Cyclopropyl A.266 O O

H H Cyclopropyl A.267 O O

H H Cyclopropyl A.268 O O

H H Cyclopropyl A.269 O O

H H Cyclopropyl A.270 O O

H H Cyclopropyl A.271 O O

H H Cyclopropyl A.272 O O

H H Cyclopropyl A.273 O O

H H C(CH₃)₂CH₂SCH₃ A.274 O O

H H C(CH₃)₂CH₂SCH₃ A.275 O O

H H C(CH₃)₂CH₂SCH₃ A.276 O O

H H C(CH₃)₂CH₂SCH₃ A.277 O O

H H C(CH₃)₂CH₂SCH₃ A.278 O O

H H C(CH₃)₂CH₂SCH₃ A.279 O O

H H C(CH₃)₂CH₂SCH₃ A.280 O O

H H C(CH₃)₂CH₂SCH₃ A.281 S S

H H C(CH₃)₂CH₂SCH₃ A.282 S S

H H C(CH₃)₂CH₂SCH₃ A.283 S S

H H C(CH₃)₂CH₂SCH₃ A.284 S S

H H C(CH₃)₂CH₂SCH₃ A.285 S S

H H C(CH₃)₂CH₂SCH₃ A.286 S S

H H C(CH₃)₂CH₂SCH₃ A.287 S S

H H C(CH₃)₂CH₂SCH₃ A.288 S S

H H C(CH₃)₂CH₂SCH₃ A.289 O S

H H C(CH₃)₂CH₂SCH₃ A.290 O S

H H C(CH₃)₂CH₂SCH₃ A.291 O S

H H C(CH₃)₂CH₂SCH₃ A.292 O S

H H C(CH₃)₂CH₂SCH₃ A.293 O S

H H C(CH₃)₂CH₂SCH₃ A.294 O S

H H C(CH₃)₂CH₂SCH₃ A.295 O S

H H C(CH₃)₂CH₂SCH₃ A.296 O S

H H C(CH₃)₂CH₂SCH₃ A.297 S O

H H C(CH₃)₂CH₂SCH₃ A.298 S O

H H C(CH₃)₂CH₂SCH₃ A.299 S O

H H C(CH₃)₂CH₂SCH₃ A.300 S O

H H C(CH₃)₂CH₂SCH₃ A.301 S O

H H C(CH₃)₂CH₂SCH₃ A.302 S O

H H C(CH₃)₂CH₂SCH₃ A.303 S O

H H C(CH₃)₂CH₂SCH₃ A.304 S O

H H C(CH₃)₂CH₂SCH₃ A.305 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.306 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.307 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.308 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.309 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.310 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.311 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.312 O O

CH₃ H C(CH₃)₂CH₂SCH₃ A.313 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.314 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.315 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.316 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.317 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.318 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.319 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.320 O O

H CH₃ C(CH₃)₂CH₂SCH₃ A.321 O O

H H C(CH₃)₂CH₂SCH₃ A.322 O O

H H C(CH₃)₂CH₂SCH₃ A.323 O O

H H C(CH₃)₂CH₂SCH₃ A.324 O O

H H C(CH₃)₂CH₂SCH₃ A.325 O O

H H C(CH₃)₂CH₂SCH₃ A.326 O O

H H C(CH₃)₂CH₂SCH₃ A.327 O O

H H C(CH₃)₂CH₂SCH₃ A.328 O O

H H C(CH₃)₂CH₂SCH₃ A.329 O O

H H C(CH₃)₂CH₂SCH₃ A.330 O O

H H C(CH₃)₂CH₂SCH₃ A.331 O O

H H C(CH₃)₂CH₂SCH₃ A.332 O O

H H C(CH₃)₂CH₂SCH₃ A.333 O O

H H C(CH₃)₂CH₂SCH₃ A.334 O O

H H C(CH₃)₂CH₂SCH₃ A.335 O O

H H C(CH₃)₂CH₂SCH₃ A.336 O O

H H C(CH₃)₂CH₂SCH₃ A.337 O O

H H C(CH₃)₂CH₂SCH₃ A.338 O O

H H C(CH₃)₂CH₂SCH₃

TABLE 1 This table discloses the 338 compounds T1.1 to T1.338 of theformula (T1)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A.

For example, the specific compound T1.23 is the compound of the formulaT1, in which each of the variables Z₁, Z₂, R₁, R₂, R₃ and R₄ has thespecific meaning given in the line A.23 of the Table A. According to thesame system, also all of the other 337 specific compounds disclosed inthe Table 1 as well as all of the specific compounds disclosed in theTables 2 to 85 are specified analogously. TABLE 2 This table disclosesthe 338 compounds T2.1 to T2.338 of the formula (T2)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 3 This table discloses the 338 compoundsT3.1 to T3.338 of the formula (T3)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 4 This table discloses the 338 compoundsT4.1 to T4.338 of the formula (T4)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 5 This table discloses the 338 compoundsT5.1 to T5.338 of the formula (T5)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 6 This table discloses the 338 compoundsT6.1 to T6.338 of the formula (T6)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 7 This table discloses the 338 compoundsT7.1 to T7.338 of the formula (T7)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 8 This table discloses the 338 compoundsT8.1 to T8.338 of the formula (T8)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 9 This table discloses the 338 compoundsT9.1 to T9.338 of the formula (T9)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 10 This table discloses the 338 compoundsT10.1 to T10.338 of the formula (T10)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 11 This table discloses the 338 compoundsT11.1 to T11.338 of the formula (T11)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 12 This table discloses the 338 compoundsT12.1 to T12.338 of the formula (T12)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 13 This table discloses the 338 compoundsT13.1 to T13.338 of the formula (T13)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 14 This table discloses the 338 compoundsT14.1 to T14.338 of the formula (T14)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 15 This table discloses the 338 compoundsT15.1 to T15.338 of the formula (T15)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 16 This table discloses the 338 compoundsT16.1 to T16.338 of the formula (T16)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 17 This table discloses the 338 compoundsT17.1 to T17.338 of the formula (T17)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 18 This table discloses the 338 compoundsT18.1 to T18.338 of the formula (T18)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 19 This table discloses the 338 compoundsT19.1 to T19.338 of the formula (T19)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 20 This table discloses the 338 compoundsT20.1 to T20.338 of the formula (T20)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 21 This table discloses the 338 compoundsT21.1 to T21.338 of the formula (T21)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 22 This table discloses the 338 compoundsT22.1 to T22.338 of the formula (T22)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 23 This table discloses the 338 compoundsT23.1 to T23.338 of the formula (T23)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 24 This table discloses the 338 compoundsT24.1 to T24.338 of the formula (T24)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 25 This table discloses the 338 compoundsT25.1 to T25.338 of the formula (T25)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 26 This table discloses the 338 compoundsT26.1 to T26.338 of the formula (T26)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 27 This table discloses the 338 compoundsT27.1 to T27.338 of the formula (T27)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 28 This table discloses the 338 compoundsT28.1 to T28.338 of the formula (T28)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 29 This table discloses the 338 compoundsT29.1 to T29.338 of the formula (T29)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 30 This table discloses the 338 compoundsT30.1 to T30.338 of the formula (T30)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 31 This table discloses the 338 compoundsT31.1 to T31.338 of the formula (T31)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 32 This table discloses the 338 compoundsT32.1 to T32.338 of the formula (T32)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 33 This table discloses the 338 compoundsT33.1 to T33.338 of the formula (T33)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 34 This table discloses the 338 compoundsT34.1 to T34.338 of the formula (T34)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 35 This table discloses the 338 compoundsT35.1 to T35.338 of the formula (T35)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 36 This table discloses the 338 compoundsT36.1 to T36.338 of the formula (T36)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 37 This table discloses the 338 compoundsT37.1 to T37.338 of the formula (T37)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 38 This table discloses the 338 compoundsT38.1 to T38.338 of the formula (T38)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 39 This table discloses the 338 compoundsT39.1 to T39.338 of the formula (T39)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 40 This table discloses the 338 compoundsT40.1 to T40.338 of the formula (T40)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 41 This table discloses the 338 compoundsT41.1 to T41.338 of the formula (T41)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 42 This table discloses the 338 compoundsT42.1 to T42.338 of the formula (T42)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 43 This table discloses the 338 compoundsT43.1 to T43.338 of the formula (T43)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 44 This table discloses the 338 compoundsT44.1 to T44.338 of the formula (T44)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 45 This table discloses the 338 compoundsT45.1 to T45.338 of the formula (T45)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 46 This table discloses the 338 compoundsT46.1 to T46.338 of the formula (T46)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 47 This table discloses the 338 compoundsT47.1 to T47.338 of the formula (T47)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 48 This table discloses the 338 compoundsT48.1 to T48.338 of the formula (T48)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 49 This table discloses the 338 compoundsT49.1 to T49.338 of the formula (T49)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 50 This table discloses the 338 compoundsT50.1 to T50.338 of the formula (T50)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 51 This table discloses the 338 compoundsT51.1 to T51.338 of the formula (T51)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 52 This table discloses the 338 compoundsT52.1 to T52.338 of the formula (T52)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 53 This table discloses the 338 compoundsT53.1 to T53.338 of the formula (T53)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 54 This table discloses the 338 compoundsT54.1 to T54.338 of the formula (T54)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 55 This table discloses the 338 compoundsT55.1 to T55.338 of the formula (T55)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 56 This table discloses the 338 compoundsT56.1 to T56.338 of the formula (T56)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 57 This table discloses the 338 compoundsT57.1 to T57.338 of the formula (T57)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 58 This table discloses the 338 compoundsT58.1 to T58.338 of the formula (T58)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 59 This table discloses the 338 compoundsT59.1 to T59.338 of the formula (T59)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 60 This table discloses the 338 compoundsT60.1 to T60.338 of the formula (T60)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 61 This table discloses the 338 compoundsT61.1 to T61.338 of the formula (T61)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 62 This table discloses the 338 compoundsT62.1 to T62.338 of the formula (T62)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 63 This table discloses the 338 compoundsT63.1 to T63.338 of the formula (T63)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 64 This table discloses the 338 compoundsT64.1 to T64.338 of the formula (T64)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 65 This table discloses the 338 compoundsT65.1 to T65.338 of the formula (T65)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 66 This table discloses the 338 compoundsT66.1 to T66.338 of the formula (T66)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 67 This table discloses the 338 compoundsT67.1 to T67.338 of the formula (T67)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 68 This table discloses the 338 compoundsT68.1 to T68.338 of the formula (T68)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 69 This table discloses the 338 compoundsT69.1 to T69.338 of the formula (T69)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 70 This table discloses the 338 compoundsT70.1 to T70.338 of the formula (T70)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 71 This table discloses the 338 compoundsT71.1 to T71.338 of the formula (T71)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 72 This table discloses the 338 compoundsT72.1 to T72.338 of the formula (T72)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 73 This table discloses the 338 compoundsT73.1 to T73.338 of the formula (T73)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 74 This table discloses the 338 compoundsT74.1 to T74.338 of the formula (T74)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 75 This table discloses the 338 compoundsT75.1 to T75.338 of the formula (T75)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 76 This table discloses the 338 compoundsT76.1 to T76.338 of the formula (T76)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 77 This table discloses the 338 compoundsT77.1 to T77.338 of the formula (T77)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 78 This table discloses the 338 compoundsT78.1 to T78.338 of the formula (T78)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 79 This table discloses the 338 compoundsT79.1 to T79.338 of the formula (T79)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 80 This table discloses the 338 compoundsT80.1 to T80.338 of the formula (T80)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 81 This table discloses the 338 compoundsT81.1 to T81.338 of the formula (T81)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 82 This table discloses the 338 compoundsT82.1 to T82.338 of the formula (T82)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 83 This table discloses the 338 compoundsT83.1 to T83.338 of the formula (T83)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 84 This table discloses the 338 compoundsT84.1 to T84.338 of the formula (T84)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 85 This table discloses the 338 compoundsT85.1 to T85.338 of the formula (T85)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 86 This table discloses the 338 compoundsT86.1 to T86.338 of the formula (T86)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 87 This table discloses the 338 compoundsT87.1 to T87.338 of the formula (T87)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 88 This table discloses the 338 compoundsT88.1 to T88.338 of the formula (T88)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 89 This table discloses the 338 compoundsT89.1 to T89.338 of the formula (T89)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 90 This table discloses the 338 compoundsT90.1 to T90.338 of the formula (T90)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A. TABLE 91 This table discloses the 338 compoundsT91.1 to T91.338 of the formula (T91)

in which, for each of these 338 specific compounds, each of thevariables Z₁, Z₂, R₁, R₂, R₃ and R₄ has the specific meaning given inthe corresponding line, appropriately selected from the 338 lines A.1 toA.338, of the Table A.

Formulation Examples % =Per Cent by Weight

EXAMPLE F1 Emulsion concentrates a) b) c) Active ingredient 25% 40% 50%Calcium dodecylbenzenesulfonate  5%  8% 6% Castor oil polyethyleneglycol ether  5% — — (36 mol of EO) Tributylphenoxypolyethylene glycolether — 12% 4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture 65%25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water. EXAMPLE F2 Solutions a) b) c) d)Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% —— — Polyethylene glycol MW 400 — 70% — — N-Methylpyrrolid-2-one — 20% —— Epoxidized coconut oil — — 1% 5% Petroleum ether (boiling range:160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops. EXAMPLE F3Granules a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin 94%  — 79%54% Highly disperse silica 1% — 13% 7% Attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo. EXAMPLE F4 Dusts a) b) Active ingredient 2% 5% Highly dispersesilica 1% 5% Talc 97%  — Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient. EXAMPLE F5 Wettable powders a) b) c) Activeingredient 25%  50%  75% Sodium lignosulfonate 5% 5% — Sodium laurylsulfate 3% — 5% Sodium diisobutylnaphthalenesulfonate — 6% 10%Octylphenoxypolyethylene glycol — 2% — ether (7-8 mol of EO) Highlydisperse silica 5% 10%  10% Kaolin 62%  27%  —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration. EXAMPLE F6 Extruder granules Active ingredient 10% Sodiumlignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air. EXAMPLE F7 Coated granules Active ingredient 3% Polyethyleneglycol (MW 200) 3% Kaolin 94%

In a mixer, the finely ground active ingredient is applied uniformly tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules. EXAMPLE F8 Suspension concentrateActive ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethyleneglycol ether (15 mol of EO) 6% Sodium lignosulfonate 10%Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2%Silicone oil (75% aqueous emulsion) 0.8% Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Biological Examples %=Per Cent by Weight, Unless Otherwise SpecifiedExample B1 Activity Against Aphis craccivora

Pea seedlings are infected with Aphis craccivora, subsequently sprayedwith a spray mixture comprising 400 ppm of active ingredient and thenincubated at 20°. 3 and 6 days later, the percentage reduction in thepopulation (% activity) is determined by comparing the number of deadaphids between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.

Example B2 Activity Against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 larvae (2nd instar) of Diabrotica balteataand introduced into a plastic container. 6 days later, the percentagereduction in the population (% activity) is determined by comparing thenumber of dead larvae between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1, T1.3, T7.1 and T7.3 have an activityof over 80%.

Example B3 Activity Against Heliothis virescens (Foliar Application)

Young soya plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (1st instar) of Heliothisvirescens and introduced into a plastic container. 6 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1, T1.3, T2.1, T7.1, T7.3, T75.1, T75.3,T76.1, T76.3, T79.1, T81.1, T2.2, T8.1, T5.1, T5.3, T20.1, T20.3, T9.1,T9.3 and T9.2 have an activity of over 80%.

Example B4 Activity Against Heliothis virescens (Application to Eggs)

Heliothis virescens eggs, which have been deposited on cotton, aresprayed with an aqueous emulsion spray mixture comprising 400 ppm ofactive ingredient. After 8 days, the percentage hatching rate of theeggs and the survival rate of the caterpillars (% activity) areevaluated in comparison with untreated control batches.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1, T1.3, T2.1, T7.1, T7.3, T75.1, T75.3,T76.1, T76.3, T79.1,T81.1, T2.2, T8.1, T5.1, T5.3, T20.1, T20.3, T9.1,T9.3 and T9.2 have an activity of over 80%.

Example B5 Activity Against Myzus persicae (Foliar Application)

Pea seedlings are infected with Myzus persicae, subsequently sprayedwith a spray mixture comprising 400 ppm of active ingredient and thenincubated at 20°. 3 and 6 days later, the percentage reduction in thepopulation (% activity) is determined by comparing the number of deadaphids between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1 and T7.1 have an activity of over 80%.

Example B6 Activity Against Myzus persicae (Systemic Application)

Pea seedlings are infected with Myzus persicae, and their roots aresubsequently placed into a spray mixture comprising 400 ppm of activeingredient. The seedlings are then incubated at 20°. 3 and 6 days later,the percentage reduction in the population (% activity) is determined bycomparing the number of dead aphids between the treated and untreatedplants.

In this test, compounds listed in the Tables 1 to 85 show good activity.

Example B7 Activity Against Plutella xylostella

Young cabbage plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (3rd instar) of Plutellaxylostella and introduced into a plastic container. 3 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1, T1.3, T2.1, T7.1, T7.3, T22.3, T75.1,T75.3, T76.1, T76.3, T78.1, T79.1, T81.1, T2.2, T8.1, T5.1, T5.3, T20.1,T20.3, T9.1, T9.3 and T9.2 have an activity of over 80%.

Example B8 Activity Against Spodoptera littoralis

Young soya plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of active ingredient and, after the spray coating hasdried on, populated with 10 caterpillars (1st instar) of Spodopteralittoralis and introduced into a plastic container. 3 days later, thepercentage reduction in the population and in the feeding damage (%activity) are determined by comparing the number of dead caterpillarsand the feeding damage between the treated and untreated plants.

In this test, compounds listed in the Tables 1 to 85 show good activity.In particular, the compounds T1.1, T1.3, T2.1, T7.1, T7.3, T75.1, T75.3,T76.1, T76.3, T2.2, T8.1, T5.1, T5.3, T20.1, T20.3, T9.1, T9.3 and T9.2have an activity of over 80%.

1. A compound of the formula

in which Z₁ is an oxygen atom; or a sulfur atom; Z₂ is an oxygen atom;or a sulfur atom; R₁ is a phenyl or naphthyl group, which is substitutedindependently by 1 or 2 substituents R_(a) and optionally furthersubstituted independently by 1 by 3 substituents R_(b); or R₁ isheteroaryl composed of a ring having 5 or 6 ring members or of acombination of at least two rings having in each case independently ofone another 5 or 6 ring members, where 1 up to and including 4 of thering members is (are) (a) heteroatoms(s) selected from the groupconsisting of nitrogen, oxygen and sulfur, which heteroaryl isunsubstituted or substituted independently by 1 or 4 substituents R_(c);R₂ is hydrogen; a C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl orC₃-C₆cycloalkyl group, which group is unsubstituted or substitutedindependently by one or more substituents, selected from the group,consisting of the substituents R_(a), C₁-C₆alkoxy; halo-C₁-C₆alkoxy;C₃-C₆cycloalkoxy; C₁-C₆alkylthio; halo-C₁-C₆alkylthio; C₁-C₆alkylamino;halo-C₁-C₆alkylamino; di-C₁-C₆alkylamino, in which the two alkyl groupsare the same or different or, taken together, form, together with thenitrogen atom, to which they are attached, a ring containing 1 ringnitrogen atom and 2 to 12 ring carbon atoms and optionally 1 furtherring hetero atom, which then replaces 1 ring carbon atom and is selectedfrom the group, consisting of an oxygen, a sulfur and a nitrogen atom,which ring is unsubstituted or substituted independently by 1 to 4substituents, selected from the group, consisting of cyano, nitro,halogen, C₁-C₄alkyl and C₁-C₄alkoxy; di-(halo-C₁-C₆alkyl)-amino, inwhich the two haloalkyl groups are the same or different;C₃-C₆cycloalkylamino; N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino;C₁-C₆alkoxycarbonyl; halo-C₁-C₆alkoxycarbonyl; C₁-C₆alkylcarbonyl orhalo-C₁-C₆alkylcarbonyl; R₄ is hydrogen; a substituent R₁; a substituentR_(e); a C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkylgroup, which group is unsubstituted or substituted independently by oneor more substituents, selected from the group, consisting of thesubstituents R_(a), the substituents R_(a) and a phenyl, benzoyl,phenoxy or heteroaryl group composed of a ring having 5 or 6 ringmembers or of a combination of at least two rings having in each caseindependently of one another 5 or 6 ring members, where 1 up to andincluding 4 of the ring members is (are) (a) heteroatoms(s) selectedfrom the group consisting of nitrogen, oxygen and sulfur, which group isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of the substituents R_(c); a groupCH₁OR₁; a group CH₂SR₁; a group CH₂NHR₁, which group is optionallyfurther substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁-C₆alkyl; C₁-C₆alkoxy; halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; agroup OR₁; C₁-C₆alkylthio; halo-C₁-C₆alkylthio; a group SR₁;C₁-C₆alkylsulfinyl; halo-C₁-C₆alkylsulfinyl; C₁-C₆alkylsulfonyl,halo-C₁-C₆alkylsulfonyl; C₁-C₆alkylamino; halo-C₁-C₆alkylamino;di-C₁-C₆alkylamino, in which the two alkyl groups are the same ordifferent or, taken together, form, together with the nitrogen atom, towhich they are attached, a ring containing 1 ring nitrogen atom and 2 to12 ring carbon atoms and optionally 1 further ring hetero atom, whichthen replaces 1 ring carbon atom and is selected from the group,consisting of an oxygen, a sulfur and a nitrogen atom, which ring isunsubstituted or substituted independently by 1 or 4 substituents,selected from the group, consisting of cyano, nitro, halogen, C₁-C₄alkyland C₁-C₄alkoxy; di-(halo-C₁-C₆alkoxy)-amino, in which the two haloalkylgroups are the same or different; C₃-C₆cycloalkylamino;N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkenyl)-amino; a group NHR₁, which group isoptionally further substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁-C₆alkyl; a group C(═O)R_(d); a group C(═O)R_(e); a groupC(═S)R_(d); or group C(═S)R_(e); or R₃ and R₄, taken together, form,together with the nitrogen atom, to which they are attached, a ringcontaining 1 ring nitrogen atom and 2 to 6 ring carbon atoms andoptionally 1 further ring hereto atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy; R_(a)is cyano; nitro; halogen; C₁-C₆alkenyl; halo-C₁-C₆alkyl;C₁-C₆alkoxy-C₁-C₆alkyl; C₂-C₆alkenyl; halo-C₂-C₆alkenyl; C₂-C₆alkynyl;halo-C₂-C₆-alkynyl; C₃-C₆-cycloalkyl; halo-C₃-C₆cycloalkyl; hydroxy;C₁-C₆alkoxy; halo-C₁-C₆alkyloxy; C₃-C₆cycloalkoxy; mercapto;C₁-C₆alkylthio; halo-C₁-C₆alkylthio; C₃-C₆alkylsulfinyl;halo-C₁-C₆alkylsulfinyl; C₁-C₆alkylsulfonyl; halo-C₁-C₆alkylsulfonyl;amino; C₁-C₆alkylamino; halo-C₁-C₆alkylamino; di-C₁-C₆alkylamino, inwhich the two alkyl groups are the same of different or taken together,form, together with the nitrogen atom, to which they are attached, aring containing 1 ring nitrogen atom and 2 to 12 ring carbon atoms andoptionally 1 further ring hetero atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;di-(halo-C₁-C₆alkyl)-amino, in which the two haloalkyl groups are thesame or different; C₃-C₈cycloalkylamino;N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino; carboxy, C₁-C₆alkoxycarbonyl;halo-C₁C-₆alkoxycarbonyl; aminocarbonyl; C₁-C₆alkylaminocarbonyl;halo-C₁C₆alkylaminocarbonyl; di-C₁-C₆alkylaminocarbonyl, in which thetwo alkyl groups are the same or different or, taken together, form,together with the nitrogen atom, to which they are attached, a ringcontaining 1 ring nitrogen atom and 2 to 12 ring carbon atoms andoptionally 1 further ring hereto atom, which then replaces 1 ring carbonatom and is selected from the group, consisting of an oxygen, a sulfurand a nitrogen atom, which ring is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;di-(halo-C₁-C₆alkyl)-aminocarbonyl, in which the two haloalkyl groupsare the same or different; C₁-C₆alkylcarbonyl; halo-C₁-C₆alkylcarbonyl;or tri-C₁-C₆alkylsilyl, in which the three alkyl groups are the same ordifferent; or 2 substituents R_(a), which are attached to adjacentcarbon atoms, taken together, are —(CH₂—)₃; —(CH₂—)₄; —(CH₂—)₅;—(CH═CH—)₂; —OCH₂O—; —O—(CH₂—)₂O—; —OCF₂O—; —(CF₂—)₂O—; —O—(CF₂—)₂; or—O—(CF₂—)₂O—; R_(c) is halogen; C₁-C₆alkyl; C₂-C₆alkenyl; C₂-C₆alkynyl;C₃-C₆cycloalkyl; C₃-C₆alkoxy; C₁-C₆alkoxycarbonyl; or a phenyl, benzyl,phenoxy or heteroaryl group composed of a ring having 5 or 6 ringmembers or of a combination of at least two rings having in each caseindependently of one another 5 or 6 ring members, where 1 up to andincluding 4 of the ring members is (are) (a) heteroatom(s) selected fromthe group consisting of nitrogen, oxygen and sulfur; which group isunsubstituted or substituted independently by 1 or 4 substituents,selected from the group, consisting of the substituents R_(a); R_(c) isa substituent R_(a); or a phenyl, benzyl, benzoyl, phenoxy or heteroarylgroup composed of a ring having 5 or 6 ring members or of a combinationof at least two rings having in each case independently of one another 5or 6 ring members, where 1 up to and including 4 of the ring members is(are) (a) heteroatom(s) selected from the group consisting of nitrogen,oxygen and sulfur, which group is unsubstituted or substitutedindependently by 1 to 4 substituents, selected from the group,consisting of the substituents R_(a); R_(d) is a substituent R₁;C₁-C₆alkyl; halo-C₁-C₆alkyl; C₁-C₆alkoxy-C₁-C₆alkyl; a group CH₂R₁; agroup CH₂OR₁; a group CH₂SR₁; a group CH₂NHR₁, which group is optionallyfurther substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁C₆alkyl; C₂-C₆alkenyl; halo-C₂-C₆alkenyl; C₂-C₆alkynyl;halo-C₂-C₆alkynyl; C₃-C₆cycloalkyl; halo-C₃-C₆cycloalkyl; C₁-C₆alkoxy;halo-C₁-C₆alkoxy; C₃-C₆cycloalkoxy; a group OR₁; C₁-C₆alkylthio;halo-C₁-C₆alkylthio; a group SR₁; C₁-C₆alkylamino; halo-C₁-C₆alkylamino;di-C₁-C₆alkylamino, in which the two alkyl groups are the same ordifferent or, taken together, form, together with the nitrogen atom, towhich they are attached, a ring containing 1 ring nitrogen atom and 2 to12 ring carbon atoms and optionally 1 further ring hetero atom, whichthen replaces 1 ring carbon atom and is selected from the group,consisting of an oxygen, a sulfur and a nitrogen atom, which ring isunsubstituted or substituted independently by 1 to 4 substituents,selected from the group, consisting of cyano, nitro, halogen, C₁-C₄alkyland C₁-C₄alkoxy; di-(halo-C₁-C₆alkoxy)-amino, in which the two haloalkylgroups are the same or different; C₃-C₆cycloalkylamino;N—(C₁-C₆alkyl)-N—(C₃-C₆cycloalkyl)-amino; or a group NHR₁, which groupis optionally further substituted at the nitrogen atom by C₁-C₆alkyl orhalo-C₁-C₆alkyl; R₆ is a carbocyclyl or heterocyclyl group, which groupis monocyclic or bicyclic and is non-aromatic, in which group 1 or 2 ofthe ring members are optionally selected from the group, consisting ofthe groups C(═O), S(═O) and S(═O)₂, and which group is unsubstituted orsubstituted independently by 1 to 4 substituents, selected from thegroup, consisting of cyano, nitro, halogen, C₁-C₄alkyl and C₁-C₄alkoxy;R₅ is hydrogen or forms, taken together with R₈ or with a monovalentsubstituent attached to that atom of R₆, via which atom R₆ is directlyconnected with the carbon atom, shown in the formula I, which carriesR₅, one additional bond; R₆ and R₇, taken together, form, together withthe two carbon atoms, shown in the formula I, to which atoms they areattached, a bicyclic ring system, which ring system is carbocyclic orheterocyclic, which ring system is substituted, in the manner shown inthe formula I, by the four substituents —N(R₂)—C(=Z₁)-R₁,—C(=Z₂)-N(R₃)—R₄, R₅ and R₈, and which ring system is optionally furthersubstituted; and R₈ is hydrogen; or a C₁-C₆alkyl group; or forms, takentogether with R₅ or with a monovalent substituent attached to that atomof R₇, via which atom R₇ is directly connected with the carbon atom,shown in the formula I, which carries R₈, one additional bond, or, whereappropriate, a tautomer thereof in each case in free form or in saltform.
 2. A compound according to claim 1 of the formula I, in which Z₁is an oxygen atom, or, where appropriate, a tautomer thereof.
 3. Acompound according to claim 1 of the formula I, in which Z₂ is an oxygenatom, or, where appropriate, a tautomer thereof.
 4. A compound accordingto claim 1 of the formula I, in which R₁ is a phenyl, pyridyl orpyrazolyl group, which is unsubstituted or substituted, or, whereappropriate, a tautomer thereof.
 5. A compound according to claim 4 ofthe formula I, in which R₁ is a pyrazol-5-yl group, which is substitutedin the 3-position by halogen, halo-C₁-C₆alkyl or halo-C₁-C₆alkoxy and inthe 1-position by a pyrid-2-yl group, which group is substituted in the3-position by chlorine or bromine, or, where appropriate, a tautomerthereof.
 6. A compound according to claim 1 of the formula I, in whichR₂ is hydrogen or C₁-C₆alkyl, or, where appropriate, a tautomer thereof.7. A compound according to claim 1 of the formula I, in which R₃ ishydrogen or C₁-C₆alkyl, or, where appropriate, a tautomer thereof.
 8. Acompound according to claim 1 of the formula I, in which R₄ isC₁-C₆alkyl, or, where appropriate, a tautomer thereof.
 9. A compoundaccording to claim 1 of the formula I, in which R₅ and R₈, takentogether, are a bond, or, where appropriate, a tautomer thereof.
 10. Acompound according to claim 1 of the formula I, in which the two carbonatoms, shown in the formula I, to which atoms R₆ and R₇ are attached,are two ring members of an aromatic ring, or, where appropriate, atautomer thereof.
 11. A pesticidal composition, which comprises at leastone compound according to claim 1 of the formula I or, whereappropriate, a tautomer thereof, in each case in free form or inagrochemically utilizable salt form, as active ingredient and at leastone auxiliary.
 12. A composition according to claim 11 for controllinginsects or representatives of the order Acarina.
 13. A method forcontrolling pests, which comprises applying a composition according toclaim 11 to the pests or their environment.
 14. A method according toclaim 13 for controlling insects or representatives of the orderAcarina.
 15. A method according to claim 13 for the protection of plantpropagation material from the attack by pests, which comprises treatingthe propagation material or the site, where the propagation material isplanted.
 16. Plant propagation material treated in accordance with themethod described in claim
 15. 17. A compound of the formula B

in which R₁, R₅, R₆, R₇ and R₈ have the meanings given in claim 1 forthe formula I, or, where appropriate, a tautomer thereof, in each casein free form or in salt form.
 18. A compound of the formula D

in which Z₁, R₁, R₂, R₅, R₆, R₇ and R₈ have the meanings given in claim1 for the formula I; and R is OH, C₁-C₄alkoxy or Cl, or, whereappropriate, a tautomer thereof, in each case in free form or in saltform.
 19. A compound of the formula AA

in which R₂, R₃, R₄, R₅, R₆, R₇ and R₈ have the meanings given in claim1 for the formula I, or, where appropriate a tautomer thereof, in eachcase in free form or in salt form.
 20. Compounds of formulae VIIa andVIIb

wherein R₀₁ is hydrogen; amino or nitro; R₀₂ is hydrogen or C₁-C₄alkyl;R₀₃ is C₁-C₄alkyl, C₁-C₄alkyl mono- or disubstituted by cyano, COOH,nitro, C₁-C₄alkoxy or cyclopropyl, C₂-C₈alkenyl, C₂-C₈alkenylsubstituted by halogen; C₁-C₄alkoxy, C₃-C₆-alkinyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl substituted byC₁-C₄alkyl, pyridyl, phenyl-C₂-C₆alkenyl or cyclopropyl; cyclobutylsubstituted by C₁-C₄alkyl; cyclopentylthio-C₁-C₄alkyl, benzyloxy,benzyloxy substituted by halogen; benzylthio-C₁-C₄alkyl, wherein thebenzyl group may itself be substituted by C₁-C₄alkyl; thiophenylsubstituted by halophenyl; phenoxy-C₁-C₄alkyl, wherein the phenyl groupmay be mono- or disubstituted by halogen; phenyl-C₁-C₄alkyl, wherein thephenyl group may itself be mono- or disubstituted by substituentsselected from halogen, nitro, benzothiazol-2-yloxy, C₁-C₄haloalkyl,C₁-C₄alkoxy and C₁-C₄alkyl; 3,4-dihydro-2H-benzo[b][1,4]dioxepinyl,1,2,3,4-tetrahydro-naphthalenyl substituted by C₁-C₄alkoxy;C₂-C₆alkenyloxy, isoxazolyl substituted by C₁-C₄alkyl; thiazolyl,C₁-C₄alkoxycarbonyl-C₁-C₄alkyl, phenyl substituted by hydroxy,halophenyloxy, C₁-C₄alkyl-silyl(C₁-C₄-alkyl)₃ or C₂-C₆alkinyl; pyridylsubstituted by C₁-C₄alkoxy; C₁-C₆alkylthio-C₁-C₄alkyl,C₂-C₆alkenylthio-C₁-C₄alkyl, C₃-C₆alkinylthio-C₁-C₄alkyl,dioxolan-2-yl-C₁-C₄alkyl, (C₁-C₄alkyl-dioxotan-2-yl)-C₁-C₄alkyl,triazolyl-C₁-C₄alkyl, thienyl-C₁-C₄alkyl, morpholinyl-C₁-C₄alkyl,C₁-C₄alkylthio-C₁-C₄alkyl, 2,3-dihydro-1H-isoindolyl,halo-substituted-thiazolyl-C₁-C₄alkyl, C₁-C₄alkylsulfony-C₁-C₄alkyl orquinolylthio-C₁-C₄alkyl, wherein the quinotine group may be substitutedby C₁-C₄haloalkyl; R₀₄ is C₁-C₄haloalkyl; R₀₅ is halogen; each of R₀₆and R₀₁₀, which may be the same or different, represents hydrogen,C₁-C₆alkyl, C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonylamino, hydroxy,cyano, halogen or C₁-C₆lkoxy, R₀₇ is hydrogen, nitro or halogen; Y₀₁ isC(R₀₈), sulfur, nitrogen or a chemical bond; R₀₈ is hydrogen, halogen,C₁-C₄alkyl or nitro; and Y₀₂ is C(R₀₉), a chemical bond, or is nitrogenor sulfur; and R₀₉ is hydrogen, phenyl, phenyl substituted by halogen,or halogen.